kSIST FprEN ISO 22854:2021

Liquid petroleum products - Determination of hydrocarbon types and oxygenates in automotive-motor gasoline and in ethanol (E85) automotive fuel - Multidimensional gas chromatography method (ISO/FDIS 22854:2021)

Flüssige Mineralölerzeugnisse - Bestimmung der Kohlenwasserstoffgruppen und der sauerstoffhaltigen Verbindungen in Ottokraftstoffen und in Ethanolkraftstoff (E85) - Multidimensionales gaschromatographisches Verfahren (ISO/FDIS 22854:2021)

Dieses Dokument legt ein Verfahren zur gaschromatographischen Bestimmung (GC) von gesättigten, olefinischen und aromatischen Kohlenwasserstoffen in Ottokraftstoffen und Ethanolkraftstoff (E85) fest. Zusätzlich können die Gehalte an Benzol und Toluol, sauerstoffhaltigen Verbindungen sowie der Gesamt¬sauerstoffgehalt bestimmt werden.
ANMERKUNG 1   Für die Zwecke dieses Dokuments wird zur Angabe des Massenanteils, w, einer Substanz der Ausdruck „% (m/m)“ und für den Volumenanteil, φ, einer Substanz der Ausdruck „% (V/V)“ verwendet.
Dieses Dokument definiert zwei Verfahren, A und B.
Verfahren A ist anwendbar für Ottokraftstoffe mit einem Gesamtaromatenanteil von 19,32 % (V/V) bis zu 46,29 % (V/V), einem Gesamtolefinanteil von 0,40 % (V/V) bis zu 26,85 % (V/V), einem Anteil an sauerstoff¬haltigen Verbindungen von 0,62 % (V/V) bis zu 9,85 % (V/V), einem Sauerstoffgehalt von 1,50 % (m/m) bis 12,32 % (m/m), einem Benzolgehalt von 0,38 % (V/V) bis zu 1,98 % (V/V) und einem Toluolgehalt von 5,85 % (V/V) bis zu 31,65 % (V/V).
Das Verfahren wurde auch für einzelne sauerstoffhaltige Verbindungen geprüft. Die Präzision wurde bestimmt für ein Gesamtvolumen an Methanol von 1,05 % (V/V) bis zu 16,96 % (V/V), ein Gesamtvolumen an Ethanol von 0,50 % (V/V) bis zu 17,86 % (V/V), ein Gesamtvolumen an MTBE von 0,99 % (V/V) bis zu 15,70 % (V/V), ein Gesamtvolumen an ETBE von 0,99 % (V/V) bis zu 15,49 % (V/V), ein Gesamtvolumen an TAME von 0,99 % (V/V) bis zu 5,92 % (V/V) und ein Gesamtvolumen an TAEE von 0,98 % (V/V) bis zu 15,59 % (V/V).
Obwohl dieses Prüfverfahren zur Bestimmung höherer Olefingehalte bis zu 50 % (V/V) angewendet werden kann, wurde die Präzision für Olefine nur im Bereich von 0,40 % (V/V) bis 26,85 % (V/V) ermittelt.
Obwohl dieses Verfahren speziell für die Analyse von Ottokraftstoffen mit sauerstoffhaltigen Verbindungen entwickelt wurde, kann es auch auf andere Kohlenwasserstoffe mit ähnlichen Siedebereichen, wie z. B. Naphthas und Reformate, angewendet werden.
ANMERKUNG 2   Für Verfahren A wurde die Anwendbarkeit dieses Dokuments auch für die Bestimmung von n Propanol, Aceton und Diisopropylether (DIPE) überprüft. Es wurden jedoch für diese Verbindungen keine Präzisionsdaten bestimmt.
Verfahren B beschreibt die Analyse von sauerstoffhaltigen Verbindungen (Ethanol, Methanol, Ether, C3- bis C5-Alkohole) in Ethanolkraftstoffen (E85) mit einem Ethanolgehalt zwischen 50 % (V/V) und 85 % (V/V). Das Benzin wird mit einer sauerstofffreien Komponente verdünnt, um den Ethanolgehalt vor der GC-Analyse auf einen Wert unter 20 % (V/V) zu senken.
Die Probe kann einschließlich der Kohlenwasserstoffe vollständig analysiert werden. Präzisionsdaten für die verdünnte Probe sind nur für die Gruppe der Sauerstoffverbindungen vorhanden.
ANMERKUNG 3   Für Verfahren B kann die Präzision für einen Ethanolanteil von etwa 50 % (V/V) bis zu 85 % (V/V) verwendet werden. Für den Ethergehalt können die Präzisionsangaben in Tabelle 6 für Proben verwendet werden, deren Ethergehalt bei mindestens 11 % (V/V) liegt. Für höhere Alkoholgehalte wurden zu wenige Daten erhalten, um eine vollständige Präzisionsangabe abzuleiten; in diesem Fall sind die Werte in Tabelle 6 nur als informativ anzusehen.
ANMERKUNG 4   Es kann eine Überlappung zwischen C9- und C10-Aromaten auftreten. Das Gesamtergebnis ist jedoch korrekt. Isopropylbenzol wird von den C8-Aromaten abgetrennt und mit den anderen C9-Aromaten erfasst.

Produits pétroliers liquides - Détermination des groupes d'hydrocarbures et des composés oxygénés de l'essence pour moteurs automobiles et du carburant pour automobiles éthanol (E85) - Méthode par chromatographie multidimensionelle en phase gazeuse (ISO/FDIS 22854:2021)

Tekoči naftni proizvodi - Določevanje vrste ogljikovodikov in oksigenatov v motornem bencinu in bencinu na osnovi etanola (E85) - Metoda multidimenzionalne plinske kromatografije (ISO/FDIS 22854:2021)

General Information

• Status: Not Published
• Public Enquiry End Date: 31-May-2020
• ICS: 71.040.50 - Physicochemical methods of analysis
• ICS: 75.160.20 - Liquid fuels
• Technical Committee: NAD - Petroleum products, lubricants and related products
• Current Stage: 5020 - Formal vote (FV) (Adopted Project)
• Start Date: 05-May-2021
• Due Date: 23-Jun-2021
• Completion Date: 07-May-2021
• Ref Project: FprEN ISO 22854 - Liquid petroleum products - Determination of hydrocarbon types and oxygenates in automotive-motor gasoline and in ethanol (E85) automotive fuel - Multidimensional gas chromatography method (ISO/FDIS 22854:2021)

RELATIONS

• Revised: SIST EN ISO 22854:2016 - Liquid petroleum products - Determination of hydrocarbon types and oxygenates in automotive-motor gasoline and in ethanol (E85) automotive fuel - Multidimensional gas chromatography method (ISO 22854:2016)
• Effective Date: 01-May-2020

Standards Content (sample)

SLOVENSKI STANDARD
oSIST prEN ISO 22854:2020
01-maj-2020
Tekoči naftni proizvodi - Določevanje vrste ogljikovodikov in oksigenatov v
motornem bencinu in bencinu na osnovi etanola (E85) - Metoda
multidimenzionalne plinske kromatografije (ISO/DIS 22854:2020)
Liquid petroleum products - Determination of hydrocarbon types and oxygenates in

automotive-motor gasoline and in ethanol (E85) automotive fuel - Multidimensional gas

chromatography method (ISO/DIS 22854:2020)
Flüssige Mineralölerzeugnisse - Bestimmung der Kohlenwasserstoffgruppen und der

sauerstoffhaltigen Verbindungen in Ottokraftstoffen und in Ethanolkraftstoff (E85) -

Multidimensionales gaschromatographisches Verfahren (ISO/DIS 22854:2020)
Produits pétroliers liquides - Détermination des groupes d'hydrocarbures et des
composés oxygénés de l'essence pour moteurs automobiles et du carburant pour

automobiles éthanol (E85) - Méthode par chromatographie multidimensionelle en phase

gazeuse (ISO/DIS 22854:2020)
Ta slovenski standard je istoveten z: prEN ISO 22854
ICS:
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
75.160.20 Tekoča goriva Liquid fuels
oSIST prEN ISO 22854:2020 en,fr,de

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

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oSIST prEN ISO 22854:2020
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oSIST prEN ISO 22854:2020
DRAFT INTERNATIONAL STANDARD
ISO/DIS 22854
ISO/TC 28 Secretariat: NEN
Voting begins on: Voting terminates on:
2020-03-13 2020-06-05
Liquid petroleum products — Determination of
hydrocarbon types and oxygenates in automotive-
motor gasoline and in ethanol (E85) automotive fuel —
Multidimensional gas chromatography method

Produits pétroliers liquides — Détermination des groupes d'hydrocarbures et des composés oxygénés de

l'essence pour moteurs automobiles et du carburant pour automobiles éthanol (E85) — Méthode par

chromatographie multidimensionelle en phase gazeuse
ICS: 75.080
THIS DOCUMENT IS A DRAFT CIRCULATED
This document is circulated as received from the committee secretariat.
FOR COMMENT AND APPROVAL. IT IS
THEREFORE SUBJECT TO CHANGE AND MAY
NOT BE REFERRED TO AS AN INTERNATIONAL
STANDARD UNTIL PUBLISHED AS SUCH.
IN ADDITION TO THEIR EVALUATION AS
ISO/CEN PARALLEL PROCESSING
BEING ACCEPTABLE FOR INDUSTRIAL,
TECHNOLOGICAL, COMMERCIAL AND
USER PURPOSES, DRAFT INTERNATIONAL
STANDARDS MAY ON OCCASION HAVE TO
BE CONSIDERED IN THE LIGHT OF THEIR
POTENTIAL TO BECOME STANDARDS TO
WHICH REFERENCE MAY BE MADE IN
Reference number
NATIONAL REGULATIONS.
ISO/DIS 22854:2020(E)
RECIPIENTS OF THIS DRAFT ARE INVITED
TO SUBMIT, WITH THEIR COMMENTS,
NOTIFICATION OF ANY RELEVANT PATENT
RIGHTS OF WHICH THEY ARE AWARE AND TO
PROVIDE SUPPORTING DOCUMENTATION. ISO 2020
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oSIST prEN ISO 22854:2020
ISO/DIS 22854:2020(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2020

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

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ISO copyright office
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ii © ISO 2020 – All rights reserved
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Contents Page

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

Introduction ..................................................................................................................................................................................................................................v

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

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

3 Terms and definitions ..................................................................................................................................................................................... 2

4 Principle ........................................................................................................................................................................................................................ 3

5 Reagents and materials ................................................................................................................................................................................. 3

6 Apparatus ..................................................................................................................................................................................................................... 4

7 Sampling ........................................................................................................................................................................................................................ 5

8 Procedure..................................................................................................................................................................................................................... 5

8.1 Conditioning .............................................................................................................................................................................................. 5

8.2 Sample preparation ............................................................................................................................................................................ 5

8.2.1 Procedure B only − Sample dilution ................................................................................................................ 5

8.2.2 Procedure A and B − Sample cooling .............................................................................................................. 5

8.3 Test sample injection volume ..................................................................................................................................................... 5

8.4 V erification of the apparatus and test conditions ..................................................................................................... 5

8.5 Validation ..................................................................................................................................................................................................... 6

8.6 Preparation of the test sample .................................................................................................................................................. 6

8.7 Preparation of the apparatus and test conditions .................................................................................................... 6

9 Calculation .................................................................................................................................................................................................................. 6

9.1 General ........................................................................................................................................................................................................... 6

9.2 Calculation as % (m/m) ................................................................................................................................................................. 6

9.3 Calculation as % (V/V) .................................................................................................................................................................... 8

9.4 Calculation of total oxygen content in % (m/m) ....................................................................................................... 9

9.5 Data report according to automotive motor gasoline specification .......................................................... 9

10 Expression of results .....................................................................................................................................................................................10

10.1 Procedure A ............................................................................................................................................................................................10

10.2 Procedure B ............................................................................................................................................................................................10

11 Precision ....................................................................................................................................................................................................................10

11.1 General ........................................................................................................................................................................................................10

11.2 Repeatability, r ....................................................................................................................................................................................10

11.3 Reproducibility, R .............................................................................................................................................................................10

12 Test report ................................................................................................................................................................................................................11

Annex A (informative) Instrument specifications ...............................................................................................................................12

Annex B (informative) Examples of typical chromatograms ....................................................................................................14

Bibliography .............................................................................................................................................................................................................................20

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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 28, Petroleum and related products, fuels

and lubricants from natural or synthetic sources.

This fourth edition cancels and replaces the third edition (ISO 22854:2016), which has been technically

revised.
The main changes compared to the previous edition are as follows:
— new examples of typical chromatograms in Annex B.

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.
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Introduction

This document is a small update of the second edition (ISO 22854:2014), which in turn was a revision

to extend the scope of the first edition. Originally ISO 22854:2008 (and its predecessor EN 14517:2004)

was used for determination of saturated, olefinic, aromatic and oxygenated hydrocarbons in automotive

motor gasoline according to European fuel specifications. Recent round-robin work has shown that the

scope of the method can be updated without alteration to include petrol with higher oxygen percentages

than mentioned in the first edition and will now be applicable for automotive motor gasoline up to and

including E10.

An interlaboratory study organized by CEN has shown that the method can also be used for high-

ethanol gasoline [also called ethanol (E85) automotive fuel], provided that the sample is diluted with a

component that will not interfere with any of the components or group of components that need to be

analysed. Details of how to perform such analysis are given in 8.2.

The derived precision data for methanol do not comply with the precision calculation as presented in

this document. No precision calculation for methanol has been established as the need for such data has

not been expressed. If methanol is present in the automotive motor gasoline sample, it is recommended

[1]

that its contents is verified by the use of an appropriate test method, for instance as given in EN 228 .

[2]
The test method described in this document is harmonized with ASTM D6839 .
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oSIST prEN ISO 22854:2020
DRAFT INTERNATIONAL STANDARD ISO/DIS 22854:2020(E)
Liquid petroleum products — Determination of
hydrocarbon types and oxygenates in automotive-
motor gasoline and in ethanol (E85) automotive fuel —
Multidimensional gas chromatography method
1 Scope

This document specifies the gas chromatographic (GC) method for the determination of saturated,

olefinic and aromatic hydrocarbons in automotive motor gasoline and ethanol (E85) automotive

fuel. Additionally, the benzene content, oxygenate compounds and the total oxygen content can be

determined.

NOTE 1 For the purposes of this document, the terms % (m/m) and % (V/V) are used to represent respectively

the mass fraction, µ, and the volume fraction, φ.
This document defines two procedures, A and B.

Procedure A is applicable to automotive motor gasoline with total aromatics of up to 50 % (V/V); total

olefins from about 1,5 % (V/V) up to 30 % (V/V); oxygenates from 0,8 % (V/V) up to 15 % (V/V); total

oxygen from about 1,5 % (m/m) to about 3,7 % (m/m); and benzene of up to 2 % (V/V). The system can

be used for ethers with 5 or more C atoms up to 22 % (V/V) but the precision has not been established

up to this level.

Although this test method can be used to determine higher-olefin contents of up to 50 % (V/V), the

precision for olefins was tested only in the range from about 1,5 % (V/V) to about 30 % (V/V).

Although specifically developed for the analysis of automotive motor gasoline that contains oxygenates,

this test method can also be applied to other hydrocarbon streams having similar boiling ranges, such

as naphthas and reformates.

NOTE 2 For Procedure A, precision data have been established for the oxygenate compounds in automotive

motor gasoline samples containing ethyl-tert-butyl ether (ETBE), methyl-tert-butyl ether (MTBE), tert-amyl-

methyl ether (TAME), iso-propanol, iso-butanol, tert-butanol, methanol and ethanol. The derived precision data

for methanol do not comply with the precision calculation as presented in this document. Applicability of this

document has also been verified for the determination of n-propanol, acetone, and di-isopropyl ether (DIPE).

However, no precision data have been determined for these compounds.

Procedure B describes the procedure for the analysis of oxygenated groups (ethanol, methanol,

ethers, C3 – C5 alcohols) in ethanol (E85) automotive fuel containing ethanol between 50 % (V/V)

and 85 % (V/V). The gasoline is diluted with an oxygenate-free component to lower the ethanol content

to a value below 20 % (V/V) before the analysis by GC. If the ethanol content is unknown, it is advisable

to use a dilution of 4:1 when analysing the sample.

The sample can be fully analysed including hydrocarbons. Precision data for the diluted sample are

only available for the oxygenated groups.

NOTE 3 For Procedure B, the precision can be used for an ethanol fraction from about 50 % (V/V) up to

85 % (V/V). For the ether fraction, the precision as specified in Table 6 can be used for samples containing at

least 11 % (V/V) of ethers. For the higher alcohol fraction, too few data were obtained to derive a full precision

statement and the data presented in Table 6 are therefore only indicative.

NOTE 4 While developing this test method, the final boiling point was limited to 215 °C.

NOTE 5 An overlap between C9 and C10 aromatics can occur. However, the total is accurate. Isopropyl benzene

is resolved from the C8 aromatics and is included with the other C9 aromatics.
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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 3170, Petroleum liquids — Manual sampling
ISO 3171, Petroleum liquids — Automatic pipeline sampling

ISO 4259, Petroleum products — Determination and application of precision data in relation to

methods of test
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.

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/
3.1
hydrocarbon group

family of hydrocarbons such as saturated hydrocarbons, olefinic hydrocarbons, etc

3.1.1
saturated hydrocarbon
saturate

type of hydrocarbon that contains no double bonds with a carbon number of 3 to 12

EXAMPLE n-Paraffins, iso-paraffins, naphthenes and poly-naphthenes.
3.1.2
olefinic hydrocarbon
olefin

type of hydrocarbon that contains double or triple bonds with a carbon number of 3 to 10

EXAMPLE n-Olefins, iso-olefins and cyclic olefins.
3.1.3
aromatic hydrocarbon
aromatic

type of cyclic hydrocarbon with alternating double and single bonds between carbon atoms forming

the rings

EXAMPLE Benzene, toluene and higher homologous series with a carbon number of 6 to 10 and naphthalenes,

with a carbon number of up to 12.
3.2
oxygenate
oxygenated compound

type of hydrocarbon that contains an oxygen group, the addition of which is allowed according to

current petrol specifications
EXAMPLE Alcohols and ethers.
Note 1 to entry: See Clause 1, Note 2.
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3.3
partial group

one carbon number in an individual group, being either a single compound like toluene or an

isomeric mixture
EXAMPLE n-Butane and iso-butane.
4 Principle

4.1 Procedure A and Procedure B use the same separation technique and analysis procedure. The

difference between the parts is that for Procedure B the sample is diluted. The diluting solvent is not

considered in the integration. This makes it possible to report the results of the undiluted sample after

normalization to 100 %.

4.2 The automotive motor gasoline sample being analysed is separated into hydrocarbon groups by

means of GC analysis using special column-coupling and column-switching procedures.

The automotive motor gasoline sample is injected into the GC system and, after vaporization, is

separated into the different groups. Detection is always done by a flame ionization detector (FID).

4.3 The mass concentration of each detected compound or hydrocarbon group is determined by

the application of relative response factors (see 9.2) to the area of the detected peaks, followed by

normalization to 100 %. For automotive motor gasoline samples containing oxygenates that cannot

be determined by this test method, the hydrocarbon results are normalized to 100 % minus the value

of oxygenates as determined by another method. The liquid volume concentration of each detected

compound or hydrocarbon group is determined by the application of density values (see 9.3) to the

calculated mass concentration of the detected peaks followed by normalization to 100 %.

IMPORTANT — It is essential to the correct execution of the method that great care be taken to

ensure that all compounds are correctly identified. This is especially true for the identification of

oxygen - containing compounds because of their wide range of response factors. It is, therefore,

highly recommended for correct identification to verify possibly unknown oxygenates using a

reference mixture that contains these pure compounds.

4.4 After this analysis, the automotive motor gasoline is separated into hydrocarbon groups and then

by carbon number. By the use of the corresponding relative response factors, the mass distributions of

the groups in the automotive motor gasoline sample can be calculated.
5 Reagents and materials
5.1 Gases

Installation of suitable moisture filters is recommended for hydrogen, helium and nitrogen lines.

5.1.1 Hydrogen, 99,995 % pure.

DANGER — Hydrogen is explosive when mixed with air at concentration between 4 % (V/V) and

75 % (V/V). See the equipment manufacturers’ manuals concerning leaks in the system.

5.1.2 Helium or nitrogen, 99,995 % pure.

The system’s operating parameters such as column and trap temperatures, carrier gas flows and valve

switching times are depending on the type of carrier gas used. The use of nitrogen as carrier gas is

not possible on all configurations. Contact the equipment manufacturer for specific information or

instructions on the use of nitrogen.
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5.1.3 Compressed air.

5.2 Vials, airtight and inert, e.g. with rubber-membrane caps covered with self-sealing polytetra-

fluoroethylene (PTFE).

5.3 Reference solutions, finished automotive motor gasoline(s) used as reference and which contain

components and concentration levels comparable to those of the test sample.

The composition of the reference solution should have been determined in a round robin or by other

methods.
DANGER — Flammable. Harmful if inhaled.

5.4 Diluting solvent, used in Procedure B, shall not interfere with any other component in gasoline

being analysed. Dodecane (C H ) or tridecane (C H ) are recommended solvents.
12 26 13 28
6 Apparatus

6.1 Gas chromatograph, computer-controlled, multidimensional GC equipment, injector, FID, suitable

columns, traps and hydrogenation catalysts, of which an example is given in Annex A.

6.2 Switching valves, suitable switching valves that are used for the transfer of compounds from one

column to the other in the gas chromatograph.
They shall have a chemically inactive surface and a small dead volume.

6.3 Traps, suitable short columns (see Annex A for an example) used for retaining certain selected

chemical groups of the automotive motor gasoline using temperature control.
The absorption of the trapped compounds shall be reversible.
EXAMPLE A typical sequence is the following:

— The alcohols and higher-boiling aromatics are absorbed in a trap (sulfate column I). The remaining aromatics

are separated from the other components by means of a polar column (for example, OV 275).

— The ethers are separated from the remaining fraction by means of another trap (sulfate column II).

— The olefins are separated from the saturates by the olefin trap (for example, silver salt) in two steps. This is

necessary due to the limited capacity of such traps to retain high amounts of butene or total olefins. If the

trap capacity is sufficient for the olefin concentration, the separation may be performed in one step.

— The remaining saturated hydrocarbons are separated into paraffins and naphthenes according to their

carbon number using a 13X molecular sieve column.

— The ethers are then eluted from the trap (sulfate column II) and separated and detected according to

boiling point.

— The olefins are desorbed from the olefin trap and hydrogenated in the Pt-column. They are separated and

detected as the corresponding saturated compounds using a 13X molecular sieve.

— The alcohols and higher-boiling aromatics are eluted from the polar column and the trap (sulfate column I),

separated using a non-polar column (for example, OV 101 methyl silicone) and detected according to

boiling point.

Examples of typical chromatograms with this order of elution of the hydrocarbon fractions are shown

in Figures B.1 and B.2. Specifically for Procedure B, a typical chromatogram is shown in Figure B.6.

IMPORTANT — Sulfur-containing compounds are irreversibly adsorbed in the olefins trap and

can reduce its capacity to retain olefins. Sulfur can also be adsorbed in the alcohol and ether-

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alcohol-aromatic traps. Although the effect of low amounts of sulfur components on the various

traps or columns is very small, it is important to exercise care with automotive motor gasoline

samples with high levels of sulfur.
7 Sampling

Unless otherwise required by national fuel specification standards or by the regulations for the

sampling of automotive motor gasoline, samples shall be taken in accordance with ISO 3170 for manual

sampling or in accordance with ISO 3171 for automatic pipeline sampling.
8 Procedure
8.1 Conditioning

Condition the apparatus according to the manufacturer’s instructions after shutdowns.

8.2 Sample preparation
8.2.1 Procedure B only − Sample dilution

The procedure as described in this subclause is used to analyse gasoline samples containing higher

amounts of ethanol such as ethanol (E85) automotive fuel with ethanol content between 50 % (V/V)

and 85 % (V/V).

As the sulfate column I trap (see Table A.1) cannot trap high amounts of ethanol, the sample shall be

diluted. The selected dilutant (5.4) shall not interfere with the analysis. The level of dilution should be

chosen in such a way that the final amount of ethanol does not exceed 20 % (V/V). If the ethanol content

is unknown, it is advised to use a dilution ratio of 4:1 when analysing the sample.

8.2.2 Procedure A and B − Sample cooling

Cool the test sample to prevent loss by evaporation. Transfer a sufficient portion of the test sample to a

vial (5.2) and immediately tightly close and seal it using the self-sealing PTFE cap (see 5.2). It is advised

to cool the test sample to a temperature between 0 °C and 5 °C.
8.3 Test sample injection volume

Size the injection volume of the test sample in such a way that the capacity of the columns is not

exceeded and that the linearity of the detector is valid.
NOTE An injection volume of 0,1 µl has proven to be satisfactory.
8.4 Verification of the apparatus and test conditions

Run the reference solution (5.3) and check for correct instrument parameters, cutting times and

grouping times. If they are not correct, adjust the apparatus to the manufacturer’s recommendations

and rerun the reference solution.

Attention should be paid to components, such as benzene, olefins and oxygenates, that are near the

boundaries of separation on the group-selective columns. Care should be taken to accurately identify

the oxygen-containing compounds. It is recommended to verify
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