EN 12177:2022

Liquid petroleum products - Unleaded petrol - Determination of benzene content by gas chromatography

This document specifies a column switching gas chromatographic method for the quantitative determination of benzene content in the range 0,05 % (V/V) to 6 % (V/V) in unleaded petrol having a final boiling point not greater than 220 °C.
The method described in this document is suitable for determining benzene in petrol, including petrol containing oxygenates up to E10 (up to 3,7 % (m/m) oxygen content), in line with the relevant EC Directives [1].
NOTE   For the purposes of this document, the terms "% (V/V)" and "% (m/m)" are used to represent respectively the volume fraction and the mass fraction.
WARNING - Use of this document might involve hazardous materials, operations and equipment. This document does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this document to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

Flüssige Mineralölerzeugnisse - Unverbleiter Ottokraftstoff - Bestimmung des Benzolgehaltes mittels Gaschromatographie

Dieses Dokument legt ein gaschromatographisches Verfahren mit Säulenschaltung zur quantitativen Bestimmung des Benzolgehaltes im Bereich von 0,05 % (V/V) bis 6 % (V/V) in unverbleitem Ottokraftstoff, dessen Siedeende nicht höher ist als 220 °C, fest.
Das in diesem Dokument beschriebene Verfahren ist zur Bestimmung von Benzol in Ottokraftstoffen, einschließlich Ottokraftstoffen, die sauerstoffhaltige Verbindungen bis zu E10 (Sauerstoffgehalt bis zu 3,7 % (m/m)) enthalten, in Übereinstimmung mit den einschlägigen EG-Richtlinien [1] geeignet.
ANMERKUNG   Für die Zwecke dieses Dokuments wird zur Angabe des Volumenanteils einer Substanz der Ausdruck „% (V/V)“ und für den Massenanteil einer Substanz der Ausdruck "% (m/m)" verwendet.
WARNUNG - Die Anwendung dieses Dokuments kann die Anwendung gefährlicher Stoffe, Arbeitsgänge und Geräte mit sich bringen. Dieses Dokument beansprucht nicht, alle damit verbundenen Sicherheitsprobleme zu behandeln. Es liegt in der Verantwortung des Anwenders dieses Dokuments, vor der Anwendung geeignete Maßnahmen für die Sicherheit und den Gesundheitsschutz zu ergreifen, und die Geltung weiterer diesbezüglicher Auflagen zu prüfen.

Produits pétroliers liquides - Essence sans plomb - Détermination de la teneur en benzène par chromatographie en phase gazeuse

Le présent document spécifie une méthode de chromatographie en phase gazeuse à commutation de colonne pour la détermination quantitative de la teneur en benzène dans la plage de 0,05 % (V/V) à 6 % (V/V) dans l'essence sans plomb dont le point d'ébullition final n'est pas supérieur à 220 °C.
La méthode décrite dans ce document est adaptée à la détermination du benzène dans l'essence, y compris l'essence contenant des composés oxygénés jusqu'à E10 (jusqu'à 3,7 % (m/m) de teneur en oxygène), conformément aux directives CE pertinentes [1].
NOTE   Pour les besoins du présent document, les termes "% (V/V)" et "% (m/m)" sont utilisés pour représenter respectivement la fraction volumique et la fraction massique.
AVERTISSEMENT — L'utilisation de ce document peut impliquer des matériaux, des opérations et des équipements dangereux. Ce document n'a pas la prétention de traiter tous les problèmes de sécurité liés à son utilisation. Il incombe à l'utilisateur de ce document d'établir des pratiques appropriées en matière de sécurité et de santé et de déterminer l'applicabilité des restrictions réglementaires avant de l'utiliser.

Tekoči naftni proizvodi - Neosvinčeni motorni bencini - Določevanje benzena s plinsko kromatografijo

Ta evropski standard določa metodo plinske kromatografije s preklopom kolon za kvantitativno določevanje benzena v razponu od 0,05 % (V/V) do 10 % (V/V) v neosvinčenem motornem bencinu, katerega končno vrelišče ne presega 220 °C. Metoda, opisana v tem standardu, je primerna za določevanje benzena v motornem bencinu, vključno z bencinom, ki vsebuje kisikove spojine, v skladu z ustreznimi direktivami EU.
Opozorilo: Pri uporabi tega standarda so lahko prisotni nevarni materiali, postopki in oprema. Ta standard ne obravnava vseh varnostnih težav, ki se navezujejo na njegovo uporabo.

General Information

• Status: Published
• Publication Date: 01-Nov-2022
• ICS: 75.160.20 - Liquid fuels
• Technical Committee: CEN/TC 19 - Petroleum products, lubricants and related products
• Drafting Committee: CEN/TC 19/WG 9 - Chromatographic test methods
• Current Stage: 6060 - Definitive text made available (DAV) - Publishing
• Start Date: 02-Nov-2022
• Due Date: 03-Jan-2023
• Completion Date: 02-Nov-2022
• Ref Project: SIST EN 12177:2023 - Liquid petroleum products - Unleaded petrol - Determination of benzene content by gas chromatography

Relations

• Replaces: EN 12177:1998/AC:2000 - Liquid petroleum products - Unleaded petrol - Determination of benzene content by gas chromatography
• Effective Date: 09-Nov-2022
• Replaces: EN 12177:1998 - Liquid petroleum products - Unleaded petrol - Determination of benzene content by gas chromatography
• Effective Date: 09-Nov-2022

Overview

EN 12177:2022 - published by CEN - defines a column-switching gas chromatographic method for the quantitative determination of benzene in unleaded petrol. The method covers benzene concentrations from 0.05 % (V/V) to 6 % (V/V) in petrol with a final boiling point ≤ 220 °C and is suitable for fuels containing oxygenates up to E10 (up to 3.7 % (m/m) oxygen). The standard replaces earlier editions and provides practical laboratory procedures, calibration and calculation methods, and precision guidance for regulatory and quality control testing.

Key topics and technical requirements

• Scope & limits: Benzene 0.05–6.0 % (V/V); petrol boiling point ≤ 220 °C; compatible with oxygenated fuels up to E10.
• Analytical principle: Two-stage capillary column separation using column switching, followed by detection with flame ionization detectors (FID). Annex A provides guidance on the switching technique.
• Apparatus:
  • Gas chromatograph with column-switching capability, programmable oven, split injector and two FIDs.
  • Two capillary columns with differing polarities to achieve resolution ≥ 1 between benzene and matrix.
  • Carrier gas: helium, nitrogen or hydrogen (≥ 99.999 % purity); gas flow control for constant flow.
• Reagents & standards:
  • Benzene reference (≥ 99.0 % m/m).
  • Solvent free of benzene (e.g., heptane).
  • Internal standard (isobutyl methyl ketone preferred); internal standard in sample: 2–5 % (m/m), ≥ 0.050 g.
• Sampling & sample prep:
  • Follow EN ISO 3170 / EN ISO 3171 for sampling.
  • Cool sample to 5–10 °C; weigh containers and components to 0.1 mg accuracy; homogenize before injection.
• Calibration & calculation:
  • Calibration factor derived from peak areas and known masses of benzene and internal standard.
  • Density of sample at 15 °C must be determined (EN ISO 3675 / EN ISO 12185 / EN ISO 3838) for volume calculations.
  • Formulas provided for converting peak areas to mass and volume and for expressing benzene as % (V/V).
• Safety: Notes about benzene toxicity and hydrogen explosion risk; users must apply appropriate safety practices.

Applications and users

• Routine fuel quality control in refineries and laboratories.
• Regulatory compliance testing for petrol specifications and EC/European directives.
• Automotive fuel suppliers, independent testing labs, environmental monitoring agencies, and standards organizations verifying benzene content in marketed gasoline, including E10 blends.

Related standards

• EN ISO 3170 - Manual sampling of petroleum liquids
• EN ISO 3171 - Automatic pipeline sampling
• EN ISO 3675 / EN ISO 3838 / EN ISO 12185 - Density determination methods
• EN 12177:2022 provides precision, repeatability and reproducibility guidance and supersedes EN 12177:1998.

Keywords: EN 12177:2022, benzene determination, unleaded petrol, gas chromatography, column switching, FID, E10, petrol testing, fuel quality.

Standards Content (Sample)

SLOVENSKI STANDARD
01-januar-2023
Nadomešča:
SIST EN 12177:1999
SIST EN 12177:1999/AC:2001
Tekoči naftni proizvodi - Neosvinčeni motorni bencini - Določevanje benzena s
plinsko kromatografijo
Liquid petroleum products - Unleaded petrol - Determination of benzene content by gas
chromatography
Flüssige Mineralölerzeugnisse - Unverbleite Ottokraftstoffe - Bestimmung des
Benzolgehaltes mittels Gaschromatographie
Produits pétroliers liquides - Essence sans plomb - Détermination de la teneur en
benzène par chromatographie en phase gazeuse
Ta slovenski standard je istoveten z: EN 12177:2022
ICS:
75.160.20 Tekoča goriva Liquid fuels
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EN 12177
EUROPEAN STANDARD
NORME EUROPÉENNE
November 2022
EUROPÄISCHE NORM
ICS 75.160.20 Supersedes EN 12177:1998
English Version
Liquid petroleum products - Unleaded petrol -
Determination of benzene content by gas chromatography
Produits pétroliers liquides - Essence sans plomb - Flüssige Mineralölerzeugnisse - Unverbleiter
Détermination de la teneur en benzène par Ottokraftstoff - Bestimmung des Benzolgehaltes mittels
chromatographie en phase gazeuse Gaschromatographie
This European Standard was approved by CEN on 16 October 2022.

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
© 2022 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 12177:2022 E
worldwide for CEN national Members.

Contents Page
European foreword . 3
1 Scope . 4
2 Normative references . 4
3 Terms and definitions . 4
4 Principle . 4
5 Reagents and materials . 5
6 Apparatus . 5
6.1 Gas chromatographic assembly . 5
7 Sampling . 6
8 Procedure . 7
8.1 Setup of the apparatus . 7
8.1.1 General. 7
8.1.2 Carrier gas . 7
8.2 Calibration . 7
8.3 Determination of density . 7
8.4 Preparation of test sample . 7
8.5 Introduction of test portion . 8
8.6 Examination of the chromatogram . 8
9 Calculation . 8
9.1 Calculation of mass of benzene in the test sample . 8
9.2 Calculation of volume of benzene in the test sample . 8
9.3 Calculation of volume of test sample . 8
9.4 Calculation of benzene content as % (V/V) . 9
10 Expression of results . 9
11 Precision . 9
11.1 General. 9
11.2 Repeatability, r . 9
11.3 Reproducibility, R . 9
12 Test report . 10
Annex A (informative) Guidance on the column switching technique . 11
A.1 Introduction . 11
A.2 General apparatus parameters for the flow switching technique . 12
A.3 Gas chromatogram . 12
Bibliography . 15

European foreword
This document (EN 12177:2022) 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.
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 May 2023, and conflicting national standards shall be
withdrawn at the latest by May 2023.
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 12177:1998.
At the time of the development of the test method, the ethanol content of gasoline was limited to
5 % (V/V) which was reflected in the scope of the test method. Since several years, fuels containing up to
10 % of ethanol (3,7 % (m/m)) are common in the European market. This revision is meant to extend the
scope of the test methods to those fuels, thus reflecting market needs.
Any feedback and questions on this document should be directed to the users’ national standards body.
A complete listing of these bodies can be found on the CEN website.
According to the CEN-CENELEC Internal Regulations, the national standards organisations 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.
1 Scope
This document specifies a column switching gas chromatographic method for the quantitative
determination of benzene content in the range 0,05 % (V/V) to 6 % (V/V) in unleaded petrol having a
final boiling point not greater than 220 °C.
The method described in this document is suitable for determining benzene in petrol, including petrol
containing oxygenates up to E10 (up to 3,7 % (m/m) oxygen content), in line with the relevant EC
Directives [1].
NOTE For the purposes of this document, the terms "% (V/V)" and "% (m/m)" are used to represent
respectively the volume fraction and the mass fraction.
WARNING — Use of this document might involve hazardous materials, operations and equipment. This
document does not purport to address all of the safety problems associated with its use. It is the
responsibility of the user of this document to establish appropriate safety and health practices and
determine the applicability of regulatory limitations prior to use.
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.
EN ISO 3170, Petroleum liquids — Manual sampling (ISO 3170)
EN ISO 3171, Petroleum liquids — Automatic pipeline sampling (ISO 3171)
EN ISO 3675, Crude petroleum and liquid petroleum products — Laboratory determination of density —
Hydrometer method (ISO 3675)
EN ISO 3838, Crude petroleum and liquid or solid petroleum products — Determination of density or
relative density — Capillary-stoppered pyknometer and graduated bicapillary pyknometer methods (ISO
3838)
EN ISO 12185, Crude petroleum and petroleum products — Determination of density — Oscillating U-tube
method (ISO 12185)
3 Terms and definitions
No terms and definitions are listed in this document.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
— IEC Electropedia: available at https://www.electropedia.org/
— ISO Online browsing platform: available at https://www.iso.org/obp/
4 Principle
The benzene-containing fraction is isolated from the sample using a capillary column and, in a second
capillary column, the benzene is separated and detected using a flame ionization detector.
NOTE 1 Some oxygenates are known to interfere with the determination of benzene using a single column gas
chromatographic method.
NOTE 2 Guidance on the column switching technique is given in Annex A.
5 Reagents and materials
Use only chemicals and reagents of recognized analytical grade.
5.1 Gases
5.1.1 Carrier gas, helium, nitrogen or hydrogen, of at least 99,999 % (V/V) purity. Any oxygen
present is removed by a chemical resin filter.
5.1.2 Hydrogen, grade suitable for flame ionization detectors.
5.1.3 Compressed air regulated for flame ionization detectors.
WARNING - Hydrogen is explosive in mixtures with air at concentrations of hydrogen ranging
approximately from 4 % (V/V) to 75 % (V/V). All joints and lines carrying hydrogen shall be made gas
tight to prevent leakage of hydrogen into a confined space.
5.2 Reagents for the preparation of calibration samples
NOTE Calibration samples will normally be combinations of benzene, solvent and a
...