EN ISO 22854:2025

SLOVENSKI STANDARD
01-april-2025
Nadomešča:
SIST EN ISO 22854:2021
Tekoči naftni proizvodi - Določanje vrste ogljikovodikov in oksigenatov v
motornem bencinu in bencinu na osnovi etanola (E85) - Metoda
multidimenzionalne plinske kromatografije (ISO 22854:2025)
Liquid petroleum products - Determination of hydrocarbon types and oxygenates in
automotive-motor gasoline and in ethanol (E85) automotive fuel - Multidimensional gas
chromatography method (ISO 22854:2025)
Flüssige Mineralölerzeugnisse - Bestimmung von Kohlenwasserstoffgruppen und
sauerstoffhaltigen Verbindungen in Ottokraftstoffen und in Ethanolkraftstoff (E85) -
Multidimensionales gaschromatographisches Verfahren (ISO 22854:2025)
Produits pétroliers liquides - Détermination des groupes d'hydrocarbures et de la teneur
en composés oxygénés de l'essence pour moteurs automobiles et du carburant éthanol
pour automobiles E85 - Méthode par chromatographie multidimensionnelle en phase
gazeuse (ISO 22854:2025)
Ta slovenski standard je istoveten z: EN ISO 22854:2025
ICS:
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
75.160.20 Tekoča goriva Liquid fuels
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EN ISO 22854
EUROPEAN STANDARD
NORME EUROPÉENNE
January 2025
EUROPÄISCHE NORM
ICS 75.080 Supersedes EN ISO 22854:2021
English Version
Liquid petroleum products - Determination of
hydrocarbon types and oxygenates in automotive-motor
gasoline and in ethanol (E85) automotive fuel -
Multidimensional gas chromatography method (ISO
22854:2025)
Produits pétroliers liquides - Détermination des Flüssige Mineralölerzeugnisse - Bestimmung von
groupes d'hydrocarbures et de la teneur en composés Kohlenwasserstoffgruppen und sauerstoffhaltigen
oxygénés de l'essence pour moteurs automobiles et du Verbindungen in Ottokraftstoffen und in
carburant éthanol pour automobiles E85 - Méthode par Ethanolkraftstoff (E85) - Multidimensionales
chromatographie multidimensionnelle en phase gaschromatographisches Verfahren (ISO 22854:2025)
gazeuse (ISO 22854:2025)
This European Standard was approved by CEN on 13 December 2024.

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, Türkiye 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
© 2025 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 22854:2025 E
worldwide for CEN national Members.

Contents Page
European foreword . 3

European foreword
This document (EN ISO 22854:2025) has been prepared by Technical Committee ISO/TC 28 "Petroleum
and related products, fuels and lubricants from natural or synthetic sources" in collaboration with
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.
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 July 2025, and conflicting national standards shall be
withdrawn at the latest by July 2025.
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.
This document supersedes EN ISO 22854:2021.
Any feedback and questions on this document should be directed to the users’ national standards
body/national committee. A complete listing of these bodies can be found on the CEN website.
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, Türkiye and the
United Kingdom.
Endorsement notice
The text of ISO 22854:2025 has been approved by CEN as EN ISO 22854:2025 without any modification.

International
Standard
ISO 22854
Fifth edition
Liquid petroleum products —
2025-01
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 de la teneur en composés oxygénés de
l'essence pour moteurs automobiles et du carburant éthanol
pour automobiles (E85) — Méthode par chromatographie
multidimensionnelle en phase gazeuse
Reference number
ISO 22854:2025(en) © ISO 2025
ISO 22854:2025(en)
© ISO 2025
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
Email: copyright@iso.org
Website: www.iso.org
Published in Switzerland
ii
ISO 22854:2025(en)
Contents Page
Foreword .iv
Introduction .v
1 Scope . 1
2 Normative references . 1
3 Terms, definitions, symbols and abbreviated terms . 1
3.1 Terms and definitions .1
3.2 Symbols and abbreviated terms .2
4 Principle . 3
5 Reagents and materials . 4
6 Apparatus . 5
7 Sampling . 6
8 Procedure . 6
8.1 Conditioning.6
8.2 Sample preparation .6
8.2.1 Procedure B only — Sample dilution .6
8.2.2 All procedures — Sample cooling .7
8.3 Test sample injection volume .7
8.4 Tuning of the apparatus (Procedure C) .7
8.5 V erification of the apparatus and test conditions .7
8.6 Validation .7
8.7 Preparation of the test sample .8
8.8 Preparation of the apparatus and test conditions .8
9 Calculation . 8
9.1 General .8
9.2 Calculation as a mass fraction in per cent .8
9.3 Calculation as a volume fraction in per cent .9
9.4 Calculation of total oxygen content in mass fraction in per cent .11
9.5 Data report according to automotive motor gasoline specifications .11
10 Expression of results .11
10.1 Procedure A and C .11
10.2 Procedure B . 12
11 Precision .12
11.1 General . 12
11.2 Repeatability, r. 12
11.3 Reproducibility, R . 12
12 Test report . 14
Annex A (informative) Instrument specifications .15
Annex B (informative) Examples of typical chromatograms .18
Bibliography .27

iii
ISO 22854:2025(en)
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 document 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).
ISO draws attention to the possibility that the implementation of this document may involve the use of (a)
patent(s). ISO takes no position concerning the evidence, validity or applicability of any claimed patent
rights in respect thereof. As of the date of publication of this document, ISO had not received notice of (a)
patent(s) which may be required to implement this document. However, implementers are cautioned that
this may not represent the latest information, which may be obtained from the patent database available at
www.iso.org/patents. ISO shall not be held responsible for identifying any or all such patent rights.
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, in collaboration with 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 accordance with the Agreement on technical cooperation between ISO and
CEN (Vienna Agreement).
This fifth edition cancels and replaces the fourth edition (ISO 22854:2021), which has been technically
revised.
The main changes are as follows:
— the Scope (Clause 1) and precision (Clause 11) have been clarified in terms of total oxygenates and
corrected for previous mistakes in oxygen and ethanol contents, as well as corrected for rounding as
required by the reporting requirements;
— a new procedure C has been implemented (and precision thereof determined by an interlaboratory
study) to allow determination of very low aromaticity, benzene, toluene and hexane contents required
for small engine petrol fuel for which CEN/TC 19 has developed a specification;
— the text has been further harmonized with ASTM D6839.
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 22854:2025(en)
Introduction
Originally, this document was used for the determination of saturated, olefinic, aromatic and oxygenated
[3]
hydrocarbons in automotive motor gasoline according to European fuel specifications, such as EN 228.
An interlaboratory study has shown that the method described in this document can be used for gasolines
with a higher concentration of oxygenated compounds, including methanol. The interlaboratory study also
provided data to calculate precision for toluene in gasoline. A further study focused on higher ether contents.
Annex B includes example chromatograms of gasolines with a variety of oxygenates, which can be used to
correctly identify these oxygenates.
Another interlaboratory study has shown that the method is applicable for gasolines with a very low content
[13]
of aromatic compounds, such as those described in EN 17867. The study delivered optimalization of a
validation step (Procedure C).
This document lays down three procedures: A, B and C. The application ranges of each are given in Table 1.
Procedure A is the normal procedure for motor gasoline, whereas Procedure B describes the procedure for
the analysis of oxygenated groups (ethanol, methanol, ethers, C3 – C5 alcohols) in ethanol (E85) automotive
fuel. Procedure C describes the analysis of small engine petrol fuel containing low contents of aromatics and
olefins.
[7]
The test method described in this document is harmonized with ASTM D6839, except for Procedure C
which focuses on European products only.

v
International Standard ISO 22854:2025(en)
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, small engine petrol and ethanol (E85) automotive
fuel. Additionally, the benzene and toluene content, oxygenated compounds and the total oxygen content can
be determined.
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.
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
3 Terms, definitions, symbols and abbreviated terms
3.1 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
ISO and IEC maintain terminology databases for use in standardization at the following addresses:
— ISO Online browsing platform: available at https:// www .iso .org/ obp
— IEC Electropedia: available at https:// www .electropedia .org/
3.1.1
hydrocarbon group
HG
family of hydrocarbons
EXAMPLE Saturated hydrocarbons (3.1.2) or olefinic hydrocarbons (3.1.3).
3.1.2
saturate
saturated hydrocarbon
type of hydrocarbon that contains no double bonds with a carbon number of 3 to 12
EXAMPLE n-paraffins, iso-paraffins, cyclo-alkanes and poly-cyclic alkanes.

ISO 22854:2025(en)
3.1.3
olefin
olefinic hydrocarbon
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.
3.1.4
aromatic
aromatic hydrocarbon
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 polycyclic
aromatic hydrocarbons, with a carbon number of up to 12.
3.1.5
oxygenate
oxygenated compound
type of hydrocarbon that contains one or more oxygen atoms, the addition of which is allowed according to
fuel specifications
EXAMPLE Alcohols and ethers.
3.2 Symbols and abbreviated terms
For the purposes of this document, the following symbols and abbreviations apply.
A total, corrected signal area for the hydrocarbon group
HG
BOB before oxygenate blending
DIPE di-isopropyl ether
E85 ethanol automotive fuel
ETBE ethyl-tert-butyl ether
FID flame ionization detector
F theoretical relative response factor of a particular carbon number for a hydrocarbon type
RR,HG
group
φ volume fraction in per cent for a hydrocarbon group
HG
GC gas chromatography
H helium
HG hydrocarbon group
ID Internal diameter
M molar mass of carbon
C
M molar mass of hydrogen
H
M molar mass of the oxygenated compound
i
M molar mass of oxygen
O
MTBE methyl-tert-butyl ether
ISO 22854:2025(en)
n number of carbon atoms in the group
C
n number of hydrogen atoms in the group
H
n number of oxygen atoms in the molecule
O
PTFE polytetrafluoroethylene
QC quality control
ρ density of the hydrocarbon group
HG
r repeatability
R reproducibility
TAEE tertiary amyl-ethyl ether
TAME tertiary amyl-methyl ether
w mass fraction in per cent for a hydrocarbon group
HG
w mass percentage of the compound in the mixture
i
X the mean of the two results being compared
4 Principle
4.1 The application ranges for each procedure are given in Table 1. All procedures specified use the same
separation technique and analysis procedure.
a
Table 1 — Application ranges for each procedure
Component or group Procedure A Procedure B Procedure C
Saturates, % (volume fraction) 26,9 – 79,3
Total aromatics, % (volume fraction) 19,3 – 46,3 0,4 – 2,7
Total olefins, % (volume fraction) 0,4 – 26,9 0,1 – 2,4
Benzene, % (volume fraction) 0,38 – 1,98 0,1 – 0,5 0,04 – 0,11
Toluene, % (volume fraction) 5,85 – 31,65
n-Hexane, % (volume fraction) 0,1 - 2,1
Total napthenes (C6-C8), % (volume
0,2 - 3,8
fraction)
b
Oxygenates , % (volume fraction) 0,61 – 27,42 0,08 – 0,86
Total oxygen content, % (mass fraction) 0,50 – 12,32 0,02 – 0,16
Methanol, % (volume fraction) 1,05 – 16,96
Ethanol, % (volume fraction) 0,50 – 17,86 > 50,0 and < 85,0 0,06 - 0,39
C3 − C5 alcohols, % (volume fraction) > 1,4 and < 6,0
Ethers, % (volume fraction) > 0,5 and < 11,0
MTBE, % (volume fraction) 1,0 – 15,7 0,01 – 0,70
ETBE, % (volume fraction) 1,0 – 15,5 0,09 – 0,73
TAME, % (volume fraction) 1,0 – 5,9
TAEE, % (volume fraction) 1,0 – 15,6
a
Empty cells indicate that the application range has not been determined.
b
Oxygenated compounds (as individual component or as total oxygenates).

ISO 22854:2025(en)
4.2 The gasoline sample being analysed is separated into hydrocarbon groups by means of GC analysis
using special column-coupling and column-switching procedures.
The 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 %.
WARNING — To ensure the method is executed correctly, it is essential to carefully verify that all
compounds are correctly identified. This is especially true for the identification of oxygenated
compounds because of their wide range of response factors. To ensure correct identification, it is
therefore highly recommended 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. Using the corresponding relative response factors, the mass distributions of the groups in
the automotive motor gasoline sample can be calculated.
4.5 Procedure A assesses the total oxygenates content and individual oxygenates. The ranges given are
considered to apply to individual oxygenated compounds or the total group of (unidentified, not further
precised) oxygenates. For Procedure A, applicability of this document has been verified for the determination
of n-propanol, acetone, and di-isopropyl ether (DIPE). However, no precision data have been determined for
these compounds.
4.6 Procedure B involves the analysis of oxygenated groups (ethanol, methanol, ethers, C3 – C5 alcohols) in
ethanol (E85) automotive fuel containing ethanol with a mass fraction of between 50 % and 85 %. Procedure
B differs from Procedure A, in that the sample is diluted with an oxygenate-free component to lower the
ethanol content to a value below 20 % before the analysis by GC. 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 %.
The sample can be fully analysed including hydrocarbons. Precision data for the diluted sample are only
available for the oxygenated groups.
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.
4.7 Procedure C is applicable to the analysis of small engine petrol fuel containing low contents of
aromatics and olefins. Procedure C differs from Procedure A, in that it requires an additional tuning step to
ensure that the individual oxygenates, aromatics and olefins are correctly identified by optimizing the pre-
column temperatures and valve settings.
5 Reagents and materials
5.1 Hydrogen, 99,995 % pure.
WARNING — Hydrogen is explosive when mixed with air at a concentration between 4 % and 75 %
volume fraction. Refer to the equipment manufacturers’ manuals concerning leaks in the system.
Installation of suitable moisture filters is recommended for hydrogen lines.

ISO 22854:2025(en)
5.2 Helium or nitrogen, 99,995 % pure.
The system’s operating parameters such as column and trap temperatures, carrier gas flows and valve
switching times depend 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.
Installation of suitable moisture filters is recommended for helium and nitrogen lines.
5.3 Compressed air.
5.4 Vials, airtight and inert, e.g. with rubber-membrane caps covered with self-sealing
polytetrafluoroethylene (PTFE).
5.5 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 an interlaboratory or proficiency
test, or by other methods.
For Procedure C, make sure that the contents of aromatics, benzene and olefins in the solution are sufficiently
low and comparable to those of the test sample.
WARNING — The reference solutions are flammable and harmful if inhaled.
5.6 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
5.7 Tuning solution, used in Procedure C, containing a mixture of oxygenates (ethanol, MTBE and ETBE)
and benzene, at levels at the end or just above those of this methods range (see Table 1) and complemented
with a base solution containing various aromatics and olefins.
As a base solution, a regular oxygen-free (BOB) refinery stream is recommended. An example of a tuning
solution is given in Table 2.
Table 2 — Example of a tuning solution composition
Component or group Content
volume fraction
%
Ethanol 0,87
MTBE 0,87
ETBE 0,87
Benzene 1,00
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.

ISO 22854:2025(en)
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 as follows:
— 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 (e.g. 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 (e.g. silver salt) in two steps. This is important
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 can be performed in one step.
— The remaining saturated hydrocarbons are separated into paraffins and cyclo alkanes (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 the 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 (e.g. OV 101 methyl silicone) and detected according to the boiling point.
Examples of typical chromatograms with this order of elution of the hydrocarbon fractions are shown
in Figures B.1 to B.4. Specifically, for Procedure B, a typical chromatogram is shown in Figure B.5. For
Procedure C, exemplary chromatograms of the tuning are shown in Figure B.6.
WARNING — Sulfur-containing compounds are irreversibly adsorbed in the olefins trap and can
reduce its capacity to retain olefins. Sulfur can also adsorb in the alcohol and ether-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 when handling automotive motor gasoline samples with
high levels of sulfur.
7 Sampling
Samples shall be taken in accordance with ISO 3170 for manual sampling or in accordance with ISO 3171 for
automatic pipeline sampling.
NOTE National fuel specification standards or legal requirements for the sampling of automotive motor gasoline
can apply.
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 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 a volume fraction of 50 % and
a volume fraction of 85 %.
As the sulfate column I trap (see Table A.1) cannot trap high amounts of ethanol, the sample shall be diluted.
The selected diluting solvent (see 5.6) shall not interfere with the analysis. The level of dilution should be

ISO 22854:2025(en)
chosen in such a way that the final amount of ethanol does not exceed a volume fraction of 20 %. If the
ethanol content is unknown, it is recommended to use a dilution ratio of 4:1 when analysing the sample.
8.2.2 All procedures — Sample cooling
Cool the test sample to prevent loss by evaporation. Transfer a sufficient portion of the test sample to a vial
(5.4) and immediately tightly close and seal it using the self-sealing PTFE cap (see 5.4). It is recommended 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 the linearity of the detector is valid.
NOTE An injection volume of 0,1 µl has proven to be satisfactory.
8.4 Tuning of the apparatus (Procedure C)
This tuning step is required for type of products using small engine petrol fuel, which are low in olefin
content and are substantially free of aromatic compounds, especially benzene. This step requires optimizing
the pre-column temperatures and valve settings.
Run the tuning solution (5.7) and check for correct instrument parameters, cutting times and grouping times.
Verify whether all individual components have been identified correctly, like the examples in Figure B.6.
Some deviation from the target values is allowed but special attention should be paid to the MTBE and
ETBE values in conjunction with the benzene value. MTBE and ETBE tend to coelute with benzene when
the precolumn temperature is too high. Lower the precolumn temperature by steps of 10 °C and rerun the
tuning solution until each component can be correctly identified.
8.5 Verification of the apparatus and test conditions
Run the reference solution (see 5.5) 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.
WARNING — 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 oxygenated compounds. It is recommended to verify the identity of possible
oxygenates using a reference material that contains the pure component of interest. Annex B shows
several chromatograms specifically for oxygenate compounds, providing evidence of their elution
times and possible interferences.
[6]
NOTE The recent study, see CEN/TR 15745, has shown that iso-propanol often eludes in two peaks.
Notwithstanding the notice of importance in 4.3, this elution can happen. In this case, it is important to identify both
peaks properly. When the peaks are correctly identified, the reproducibility in 11.3 applies.
8.6 Validation
Reprocess the validation reference solution (see 5.5) and compare the obtained results with the consensus
values. The absolute deviation from the consensus values shall not be greater than the reproducibility for
the parameters given in Clause 11.
It is strongly recommended to run the validation reference solution weekly to check the proper functioning
of the equipment.
The validation reference solution(s) should contain the components in amounts similar to those found in the
test samples. Validation of the apparatus should be performed prior to the analysis of any new oxygenates.

ISO 22854:2025(en)
8.7 Preparation of the test sample
Prepare the test sample as specified in 8.2.
8.8 Preparation of the apparatus and test conditions
Set up the apparatus in accordance with 8.1 and check it in accordance with 8.5.
For Procedure C, check the areas in between the fractions on “unexpected peaks”. These can be components
eluting in the wrong fraction and adjustment of the temperature(s) can be required. Also check peak shapes,
such as double peaks or skewed peaks, which can indicate an incorrect elution order. Adjust the valve times
using the tuning and reference solutions.
9 Calculation
9.1 General
For Procedure A and C, 9.2 to 9.5 shall be followed.
For Procedure B, in the final calculations, the peak area of the diluting solvent (see 5.6) shall not be
integrated. This is so that the final report, after normalization to 100 %, gives the results for all groups and
components for the undiluted sample.
NOTE Analysing high-ethanol samples using this application can require specific analysis and reporting
procedures and competences (see manufacturer’s instructions).
9.2 Calculation as a mass fraction in per cent
The integrated peak areas are employed for the calculations. The peaks are arranged according to their
presence in the hydrocarbon group. Tables 3 and 4 give the relative response factors of hydrocarbon groups
and for oxygenated compounds.
NOTE The response factors are normalized to methane and those for the oxygenated compounds have been
determined experimentally.
After correcting with the relative response factors, the mass contributions for all hydrocarbon groups are
calculated and normalized to a mass fraction of 100 %. The hydrocarbon groups are then classified according
to the hydrocarbon type and carbon number.
Table 3 — FID relative response factors of hydrocarbon groups
Relative response factor
F
RR,HG
Carbon number
Paraffins, Cyclo-alkanes Olefins, Olefins, cyclics Aromatics
(naphthenes)
n- plus iso- n- plus iso-
3 0,916 — 0,916 — —
4 0,906 — 0,906 — —
5 0,899 0,874 0,899 0,874 —
6 0,895 0,874 0,895 0,874 0,811
7 0,892 0,874 0,892 0,874 0,820
8 0,890 0,874 0,890 0,874 0,827
9 0,888 0,874 0,888 0,874 0,832
10 0,887 0,874 0,887 0,874 0,837
11+ 0,887 — — — 0,840
ISO 22854:2025(en)
Table 4 — FID relative response factors for oxygenated compounds
Relative response factor
Oxygenated compound
F
RR,HG
MTBE 1,334
DIPE 1,317
ETBE 1,242
TAME 1,242
Methanol 3,000
Ethanol 1,870
n-propanol 1,867
iso-propanol 1,742
n-butanol 1,546
iso-butanol 1,390
sec-butanol 1,390
tert-butanol 1,230
2-methyl-2-butanol 1,400
If single compounds, e.g. oxygenate compounds, are determined by a different but accepted method, e.g.
[4] [8] [5] [9]
EN 1601, ASTM D4815, EN 13132, or ASTM D5599, they shall be excluded from integration. The
total area is then not normalized to 100 %, but to 100 % minus the excluded quantified component. The
external quantification shall be noted in the report.
Calculate the theoretical relative response factors, F , of a particular carbon number for a hydrocarbon
RR,HG
type group (response of methane set to unity) as given in Formula (1); (see Tables 1 and 2):
[]()Mn⋅ +⋅()Mn ⋅0,7487
CC HH
F = (1)
RR,HG
Mn⋅
CC
where
M is the molar mass of carbon, equal to 12,011, in g/mol;
C
n is the number of carbon atoms in the group;
C
M is the molar mass of hydrogen, equal to 1,008, in g/mol;
H
n is the number of hydrogen atoms in the group;
H
0,748 7 is the correction factor to set the response of methane to unity.
For each hydrocarbon group (HG) the mass fraction in per cent, w , is calculated as given in Formula (2):
HG
100⋅⋅AF
HG RR,HG
w = (2)
HG
()AF⋅
∑ HG,iiRR,HG,
i
where A is the total, corrected signal area for the hydrocarbon group (HG).
HG
9.3 Calculation as a volume fraction in per cent
The conversion from mass fraction to volume fraction is done using the density of the hydrocarbon groups. The
density values at 15 °C of hydrocarbon groups, expressed in kilograms per cubic metre, are shown in Table 5.
The density values of oxygenate compounds at 15 °C are shown in Table 6 (derived from Reference [10]).

ISO 22854:2025(en)
Table 5 — Density at 15 °C of hydrocarbon groups
Density
ρ
HG
Carbon
kg/m
number
Paraffins, Cyclo-alkanes Olefins, Olefins, Aromatics
n- plus iso- (naphthenes) n- plus iso- cyclics
3 506,5 — 520,4 — —
4 577,9 — 613,7 — —
5 626,9 750,3 656,5 773,3 —
6 662,2 760,6 685,9 785,3 884,3
7 688,8 762,1 704,0 790,5 871,6
8 708,4 780,5 719,3 805,2 871,9
9 728,1 792,5 738,2 812,5 878,0
10 734,0 812,8 748,6 817,6 892,8
11+ 759,0 — — — 894,4
SOURCE: Reference [10], reproduced with the permission of the authors.
Table 6 — Density at 15 °C of oxygenated compounds
Oxygenated compound Density
ρ
HG
kg/m
MTBE 745,3
DIPE 729,2
ETBE 745,6
TAME 775,2
Methanol 795,8
Ethanol 794,8
n-propanol 813,3
iso-propanol 789,5
n-butanol 813,3
iso-butanol 805,8
s
...