SIST EN 15199-3:2021

Petroleum products - Determination of boiling range distribution by gas chromatography method - Part 3: Crude oil

This document describes a method for the determination of the boiling range distribution of petroleum products by capillary gas chromatography using flame ionization detection. The standard is applicable to crude oils. The boiling range distribution and recovery to C100 or C120 can be determined.
Two procedures are described: single and dual analysis mode. The basis of each is the calculation procedure as described in Annex A.
Procedure A (or Single analysis mode) determines the boiling range through C100 or C120 in a single analysis.
Procedure B (or Dual analysis mode) combines procedure A with the boiling point distribution from C1 up to C9 using the Detailed Hydrocarbon Analysis (DHA) according EN 15199-4. The results of both analyses are merged into one boiling point distribution.
NOTE 1 There is no specific precision statement for the combined results obtained by procedure B. For the precision of the boiling range distribution according to procedure B the precision statements of procedure A and EN 15199-4 apply. No precision has been determined for the results after merging.
NOTE 2 For the purpose of this document, the terms "% (m/m)" and "% (V/V)" are used to represent the mass fraction, μ, and the volume fraction, φ, of a material respectively.
WARNING - Use of this document may 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 standard to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to use.

Mineralölerzeugnisse - Gaschromatographische Bestimmung des Siedeverlaufes - Teil 3: Rohöle

Dieses Dokument beschreibt ein Verfahren zur Bestimmung des Siedeverlaufes in Mineralölerzeugnissen mit Hilfe der Kapillar-Gaschromatographie unter Verwendung eines Flammenionisationsdetektors (FID). Diese Norm ist anwendbar auf Rohöle. Die Bestimmung des Siedeverlaufes und der Wiederfindung kann bis zu C100 oder bis zu C120 vorgenommen werden.
Es werden zwei Verfahren für die Analyse beschrieben, ein Einzelmodus und ein Dualmodus. Für beide gilt das in Anhang A beschriebene Rechenverfahren.
Bei Verfahren A (oder Einzelmodus) wird der Siedebereich durchgehend bis C100 oder C120 mittels einer einzigen Analyse ermittelt.
Verfahren B (oder Dualmodus) kombiniert Verfahren A mit der Siedepunktverteilung von C1 bis zu C9 unter Anwendung der detaillierten Kohlenwasserstoffanalyse (en: Detailed Hydrocarbon Analysis, DHA) nach EN 15199 4. Die Ergebnisse beider Analysen werden in einer Siedepunktverteilung zusammengeführt.
ANMERKUNG 1 Es gibt keine spezielle Präzisionsangabe für die durch Verfahren B erhaltenen kombinierten Ergebnisse. Für die Präzision des Siedeverlaufs nach Verfahren B gelten die Präzisionsangaben von Verfahren A und EN 15199 4. Für die Ergebnisse nach dem Zusammenführen wurde keine Präzision bestimmt.
ANMERKUNG 2 Für die Anwendung dieses Dokuments wird zur Angabe des Massenanteils, μ, einer Substanz der Ausdruck „% (m/m)“ und für den Volumenanteil, φ, einer Substanz der Ausdruck „% (V/V)" 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 dieser Norm, vor der Anwendung angemessene Maßnahmen im Hinblick auf Sicherheit und Gesundheit zu ergreifen und die Anwendbarkeit einschränkender Vorschriften zu ermitteln.

Produits pétroliers - Détermination de la répartition dans l'intervalle de distillation par méthode de chromatographie en phase gazeuse - Partie 3: Pétrole brut

Le présent document décrit une méthode pour la détermination de la répartition dans l’intervalle de distillation des produits pétroliers par chromatographie en phase gazeuse capillaire avec détection par ionisation de flamme. Cette norme s’applique aux pétroles bruts. La répartition dans l’intervalle de distillation et la récupération jusqu'à C100 ou C120 peuvent être réalisées.
Deux modes opératoires sont décrits : le mode d’analyse unique et le mode d'analyse double. Ils sont tous deux basés sur la procédure de calcul décrite en Annexe A.
Le mode opératoire A (ou mode d'analyse unique) détermine l’intervalle de distillation jusqu'à C100 ou C120 en une seule analyse.
Le mode opératoire B (ou mode d'analyse double) combine le mode opératoire A avec la répartition des points de distillation de C1 à C9 en utilisant l'analyse détaillée des hydrocarbures (DHA) selon l'EN 15199-4. Les résultats des deux analyses sont fusionnés en une seule répartition des points de distillation.
NOTE 1 Il n'y a pas de fidélité spécifique pour les résultats combinés obtenus selon le mode opératoire B. Pour la fidélité de la répartition dans l’intervalle de distillation selon le mode opératoire B, les valeurs de fidélité établies pour le mode opératoire A et l'EN 15199-4 s'appliquent. Aucune fidélité n'a été déterminée pour les résultats après le fusionnement.
NOTE 2 Pour les besoins du présent document, les termes "% (m/m)" et "% (V/V)" sont utilisés pour représenter respectivement la fraction massique, μ, et la fraction volumique, φ, des produits.
AVERTISSEMENT - L’utilisation du présent document implique l’utilisation de produits, d’opérations et d’équipements à caractère dangereux. Le présent document n’a pas la prétention d’aborder tous les problèmes de sécurité concernés par son usage. Il est de la responsabilité de l’utilisateur d’établir des règles de sécurité et d’hygiène appropriées et de déterminer l’applicabilité des restrictions réglementaires avant utilisation.

Naftni proizvodi - Določanje porazdelitve območja vrelišč z metodo plinske kromatografije - 3. del: Surova nafta

General Information

• Status: Published
• Public Enquiry End Date: 01-Dec-2019
• Publication Date: 26-Jan-2021
• ICS: 71.040.50 - Physicochemical methods of analysis
• ICS: 75.040 - Crude petroleum
• Technical Committee: NAD - Petroleum products, lubricants and related products
• Current Stage: 6060 - National Implementation/Publication (Adopted Project)
• Start Date: 06-Jan-2021
• Due Date: 13-Mar-2021
• Completion Date: 27-Jan-2021
• Ref Project: EN 15199-3:2020 - Petroleum products - Determination of boiling range distribution by gas chromatography method - Part 3: Crude oil

Relations

• Replaces: SIST EN 15199-3:2008 - Petroleum products - Determination of boiling range distribution by gas chromatography method - Part 3: Crude oil
• Effective Date: 01-Mar-2021

Overview

EN 15199-3:2020 (CEN) specifies a capillary gas chromatography (GC) method with flame ionization detection (FID) for determining the boiling range distribution of crude oil. The method simulates distillation (simulated distillation) by eluting hydrocarbons in order of increasing boiling point and reporting distributions and recoveries up to C100 or C120 (final boiling point endpoints). The standard describes two operation modes (single and dual analysis) and defines calculation algorithms and performance checks.

Key topics and requirements

• Scope and purpose: Applicable to crude oils with IBP below 100 °C and FBP above 750 °C; derives boiling point vs. percent composition using retention time calibration.
• Instrumentation: Capillary (open tubular) GC with non‑polar methyl silicone stationary phase and FID. High‑purity carrier gas (He, N2 or H2) and proper FID fuels/air required.
• Sample handling: Aliquot dilution with viscosity‑reducing solvent, controlled injection and oven temperature program (linear ramp) to separate hydrocarbon fractions.
• Analysis modes:
  • Procedure A (Single analysis mode): Full boiling range to C100/C120 in one GC run; includes quench correction for co‑eluting solvent regions.
  • Procedure B (Dual analysis mode): Combines Procedure A with a Detailed Hydrocarbon Analysis (DHA) per EN 15199-4 for C1–C9; results are merged into one distribution (merging algorithm in Annex D). Note: no precision statement exists for merged results - precision of individual methods applies.
• Calculations and reporting: Normative calculation procedure in Annex A; slice‑integration (area slices), corrected cumulative areas, recovery, IBP/FBP definitions (e.g., IBP at 0.5% and FBP at 99.5% cumulative).
• Quality and performance: System performance checks and calibration using normal alkanes (see Annex C and E). Reference to harmonization with IP 545 and ASTM D7169.
• Safety: Use involves hazardous materials (e.g., carbon disulfide); users must apply appropriate safety and regulatory controls.

Applications and users

• Practical applications:
  • Characterizing crude oil distillation behavior for refinery process design and product allocation.
  • Quality control and batch comparison of crude feeds.
  • Input data for simulation models and product yield forecasting.
• Who uses it:
  • Refinery laboratories, petroleum testing labs, analytical service providers, and R&D teams working on crude evaluation and process modelling.

Related standards

• EN 15199-1 (middle distillates & base oils)
• EN 15199-2 (heavy distillates & residual fuels)
• EN 15199-4 - Detailed Hydrocarbon Analysis (DHA) for light fractions (used in Procedure B)
• Harmonized with IP 545 and ASTM D7169

Keywords: EN 15199-3:2020, boiling range distribution, gas chromatography, crude oil, capillary GC, flame ionization detection, simulated distillation, DHA, C100, C120.

Standards Content (Sample)

SLOVENSKI STANDARD
01-marec-2021
Nadomešča:
SIST EN 15199-3:2008
Naftni proizvodi - Določanje porazdelitve območja vrelišč z metodo plinske
kromatografije - 3. del: Surova nafta
Petroleum products - Determination of boiling range distribution by gas chromatography
method - Part 3: Crude oil
Mineralölerzeugnisse - Gaschromatographische Bestimmung des Siedeverlaufes - Teil
3: Rohöle
Produits pétroliers - Détermination de la répartition dans l'intervalle de distillation par
méthode de chromatographie en phase gazeuse - Partie 3: Pétrole brut
Ta slovenski standard je istoveten z: EN 15199-3:2020
ICS:
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
75.040 Surova nafta Crude petroleum
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EN 15199-3
EUROPEAN STANDARD
NORME EUROPÉENNE
December 2020
EUROPÄISCHE NORM
ICS 75.080 Supersedes EN 15199-3:2008
English Version
Petroleum products - Determination of boiling range
distribution by gas chromatography method - Part 3:
Crude oil
Produits pétroliers - Détermination de la répartition Mineralölerzeugnisse - Gaschromatographische
dans l'intervalle de distillation par méthode de Bestimmung des Siedeverlaufes - Teil 3: Rohöle
chromatographie en phase gazeuse - Partie 3 : Pétrole
brut
This European Standard was approved by CEN on 23 November 2020.

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, Turkey 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
© 2020 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 15199-3:2020 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 . 6
5 Reagents and materials . 7
6 Apparatus . 10
7 Sampling . 11
8 Preparation of the apparatus . 12
8.1 Gas chromatograph preparation . 12
8.2 System performance check . 12
9 Corrected sample and reference material preparation . 12
10 Calibration . 13
11 Procedure . 15
12 Visual inspection of the chromatograms . 15
12.1 Blank run . 15
12.2 Reference material . 16
12.3 Sample run . 16
13 Calculation . 16
14 Expression of results . 17
15 Precision . 17
15.1 General. 17
15.2 Repeatability . 17
15.3 Reproducibility . 17
16 Test report . 19
Annex A (normative) Calculation procedure . 20
Annex B (informative) Additional guidance for the calculation algorithm . 23
Annex C (normative) System performance check . 27
Annex D (normative) Algorithm for merging boiling point distribution results of EN 15199-3
and EN 15199-4 . 29
Annex E (informative) Boiling points of normal alkanes . 37
Bibliography . 39

European foreword
This document (EN 15199-3:2020) 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 June 2021, and conflicting national standards shall be
withdrawn at the latest by June 2021.
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 15199-3:2008.
The main changes in this edition are:
—  the algorithm for merging the results of the light end analysis and the simulated distillation analysis
has been added as an informative annex;
—  additional information on the determination of the IBP and FBP is added to help the user to improve
the test results.
EN 15199 consists of the following parts, under the general title Petroleum products — Determination of
boiling range distribution by gas chromatography method:
— Part 1: Middle distillates and lubricating base oils
— Part 2: Heavy distillates and residual fuels
— Part 3: Crude oil
— Part 4: Light fraction of crude oil
This document describes the determination of boiling range distribution of materials with initial boiling
points (IBP) below 100 °C and final boiling points (FBP) above 750 °C. For testing materials with initial
boiling points (IBP) above 100 °C and final boiling point (FBP) below 750 °C, Part 1 of the standard may
be used. For testing materials with initial boiling points (IBP) above 100 °C and final boiling point (FBP)
above 750 °C, Part 2 of the standard may be used. Part 4 is used for the determination of the boiling range
distribution of hydrocarbons up to n-nonane in crude oil.
This document is harmonized with IP 545 [6] and ASTM D 7169 [4].
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, Turkey and the United
Kingdom.
1 Scope
This document describes a method for the determination of the boiling range distribution of petroleum
products by capillary gas chromatography using flame ionization detection. The standard is applicable to
crude oils. The boiling range distribution and recovery to C or C can be determined.
100 120
Two procedures are described: single and dual analysis mode. The basis of each is the calculation
procedure as described in Annex A.
Procedure A (or Single analysis mode) determines the boiling range through C or C in a
100 120
single analysis.
Procedure B (or Dual analysis mode) combines procedure A with the boiling point distribution from C
up to C using the Detailed Hydrocarbon Analysis (DHA) according EN 15199-4. The results of both
analyses are merged into one boiling point distribution.
NOTE 1 There is no specific precision statement for the combined results obtained by procedure B. For the
precision of the boiling range distribution according to procedure B the precision statements of procedure A and
EN 15199-4 apply. No precision has been determined for the results after merging.
NOTE 2 For the purpose of this document, the terms “% (m/m)” and “% (V/V)” are used to represent the mass
fraction, µ, and the volume fraction, φ, of a material respectively.
WARNING — Use of this document may 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 standard to establish appropriate safety and health practices and to
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 15199-4, Petroleum products — Determination of boiling range distribution by gas chromatography
method — Part 4: Light fractions of crude oil
EN ISO 3170, Petroleum liquids — Manual sampling (ISO 3170)
EN ISO 3171, Petroleum liquids — Automatic pipeline sampling (ISO 3171)
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:
— IEC Electropedia: available at http://www.electropedia.org/
— ISO Online browsing platform: available at https://www.iso.org/obp
NOTE Explanation of some of the terms is given in Figure 1.
3.1
initial boiling point
IBP
temperature corresponding to the retention time at which a net area (3.9) count equal to 0,5 % of the
total sample area (3.8) under the chromatogram is obtained (see Figure 1)

Key
1 start of elution
2 initial boiling point (IBP), 3.1
3 final boiling point (FBP), 3.2
4 end of elution
Figure 1 — Typical chromatogram
3.2
final boiling point
FBP
temperature corresponding to the retention time at which a net area (3.9) count equal to 99,5 % of the
total sample area (3.8) under the chromatogram is obtained (see Figure 1)
Note 1 to entry: If the found recovery is less than 99,5 %, the final boiling point is reported as > 720 °C or > 750 °C
at that recovery.
3.3
area slice
area resulting from the integration of the chromatographic detector signal within a specified retention
time interval
Note 1 to entry: In area slice mode peak detection parameters are bypassed and the detector signal integral is
recorded as area slices of consecutive, fixed duration time interval.
3.4
corrected area slice
area slice (3.3) corrected for baseline offset by subtraction of the exactly corresponding area slice in a
previously recorded blank (non-sample) analysis
3.5
cumulative corrected area
accumulated sum of corrected area slices (3.4) from the beginning of the analysis through a given
retention time, ignoring any non-sample area for example of solvent
3.6
slice width
time interval used to integrate the continuous (analogue) chromatographic detector response during an
analysis
Note 1 to entry: The slice rate is expressed in seconds.
3.7
slice time
analysis time associated with each area slice throughout the chromatographic analysis
Note 1 to entry: The slice time is the time at the end of each contiguous area slice.
3.8
total sample area
cumulative corrected area (3.5), from the initial area point to the final area point, where the
chromatographic signal has returned to baseline after complete sample elution
3.9
net area
cumulative area counts for the sample minus the cumulative area count for the blank
3.10
recovery
ratio of the cumulative area counts of the sample to that of the reference material (external standard)
corrected for dilution and material weights combined with the percentage of light ends, if applicable
4 Principle
The boiling range distribution determination by distillation is simulated by the use of gas
chromatography. A non-polar open tubular (capillary) gas chromatographic column is used to elute the
hydrocarbon components of the sample in order of increasing boiling point.
A sample aliquot is diluted with a viscosity reducing solvent and introduced into the chromatographic
system. Sample vaporization is provided by separately heating the point of injection or in conjunction
with column oven heating.
The column oven temperature is raised at a specified linear rate to affect separation of the hydrocarbon
components in order of increasing boiling point. The elution of sample components is quantitatively
determined using a flame ionization detector. The detector signal is recorded as area slices for
consecutive retention time intervals during the analysis.
Retention times of known normal paraffin hydrocarbons, spanning the scope of the test method, are
determined and correlated to their boiling point temperatures. The normalized cumulative corrected
sample areas (3.5) for each consecutive recorded time interval are used to calculate the boiling range
distribution. The boiling point temperature at each reported percent off increment is calculated from the
retention time calibration following Annex A and the recovery (3.10) at 720 °C (C ) or 750 °C (C ) is
100 120
determined.
NOTE Further guidance on the algorithm used is given in Annex B.
Two procedures are described in this document:
— Procedure A, Single analysis mode: The boiling range can be determined by a single analysis, but with
a modified (quench corrected) detector response for those components that co-elute with the sample
diluent. A quench compensation calculation procedure is described in C.5;
— Procedure B, Dual analysis mode: This is an extension to the Procedure A method, where
Procedure A is used to determine the boiling point distribution from C through C or C . The
9 100 120
extension to an analysis of the front end of the sample (including the quenched co-elution region) is
achieved by a second analysis. This so-called Detailed Hydrocarbon Analysis (DHA) is used to
determine the boiling point distribution from C up to C . The results from Procedure A and DHA
1 9
analysis are merged using the calculation procedure described in Annex D. Procedure B does not use
the compensation calculation procedure given in C.5.
Procedure A (Single Analysis Mode): Cryogenic Initial Column Temperature (see Table 2) is preferred to
improve resolution of low boiling components.
Procedure B (Dual Analysis Mode): Ambient Initial Column Temperature is used on the analyser as the
low boiling components (C to C ) are analysed on the DHA system.
1 9
5 Reagents and materials
Unless otherwise stated, only chemicals of recognized analytical quality shall be used.
5.1 Liquid stationary phase, a methyl silicone stationary phase for the column.
5.2 Carrier gases, helium, nitrogen or hydrogen, with a purity no less than 99,999 % (V/V), and any
oxygen present removed by a chemical resin filter.
WARNING — Follow the safety instructions from the filter supplier.
5.3 Hydrogen, grade suitable for flame ionization detectors.
5.4 Compressed air, regulated for flame ionization detectors.
5.5 Alkanes, normal alkanes with a purity of at least 98 % (m/m) from C to C , C , C , C , C , C ,
5 10 12 14 16 18 20
C and C to be used with Polywax (see 5.6).
24 28
NOTE The calibration mixture from ISO 3924 [3] is also suitable.
5.6 Polywax 655 or 1000
5.7 Carbon disulfide (CS ), with a purity of no less than 99,7 % (V/V).
WARNING — Extremely flammable and toxic by inhalation.
To confirm the suitability of the carbon disulfide as a solvent, it is recommended to check elution profiles
(see Figure 2).
Figure 2 — Example of a good (A) and a bad (B) carbon disulfide solvent peak shape, obtained
under cryogenic conditions
5.8 Calibration mixture
The mixture shall contain at least one normal alkane with a boiling point lower than the IBP of the sample,
and at least one normal alkane with a boiling point close to the temperature at which the recovery is
measured.
Dissolve 0,1 g of Polywax (5.6) in 7 ml carbon disulfide (5.7), warming gently if necessary. Prepare an
equal volume mixture of alkanes (5.5) and add 10 µl to the Polywax solution.
NOTE 1 Commercially available alkane standards are suitable for column performance checks.
NOTE 2 The calibration mix is used to determine the column resolution, skewness (see C.4) of the C peak, and
retention time versus boiling point calibration curve.
NOTE 3 For the DHA front end analysis, the calibration points are taken from the sample or a suitable calibration
mixture.
5.9 Reference materials (RM)
5.9.1 A reference material has two functions:
— External standard: to determine the recovery of samples by comparing the total sample area (3.8) of
the reference material with the total sample area of the unknown sample (A.9.3);
— Boiling Point Distribution standard: to check the proper functioning of the system by comparing the
results with a known boiling point distribution on a routine basis. Typical example is given in (5.9.2).
5.9.2 Reference Material 5010, a reference sample that has been analysed by laboratories
participating in the test method cooperative study. Consensus values for the boiling range distribution of
this sample are given in Table 1.
NOTE Consensus values of newer batches can differ from the ones in Table 1, for those we refer to the sample
certificate.
5.9.3 Cyclohexane, (C H )—(99+ % pure), may be used in place of CS for the preparation of the
6 12 2
calibration mixture.
5.9.4 Binary gravimetric blend, a binary distillate mixture with boiling point ranges that gives a
baseline at the start, a baseline between the two peaks and an end of the chromatogram as possible (see
Figure 3 and B.3). This mixture is used to check the relative response of the two distillates and to check
the baselines at the start, middle and end of the chromatogram.
Table 1 —Reference Material 5010
% OFF Average Allowable deviation
°C ± °C
IBP 428 9
5 477 3
10 493 3
15 502 3
20 510 3
25 518 4
30 524 4
35 531 4
40 537 4
45 543 4
50 548 5
55 554 4
60 560 4
65 566 4
70 572 4
75 578 5
80 585 4
85 593 4
90 602 4
95 616 4
FBP 655 18
Key
X retention time (min)
Y response
Figure 3 — Typical chromatogram of binary gravimetric blend distillate
6 Apparatus
6.1 Gas chromatograph, with the following performance characteristics.
6.1.1 Flame ionization detector, connected to the column so as to avoid any cold spots. The detector
shall be capable of operating at a temperature at least equivalent to the maximum column temperature
employed in the method. The capillary column should sit just below the flame tip and it is recommended
that the orifice of the jet should be 0,6 mm minimum to prevent frequent blocking with silicones.
6.1.2 Column temperature programmer, capable of linear programmed temperature operation over
the range mentioned in Table 2.
6.2 Column
Use a metal column, 0,53 µm inner diameter coated with methyl silicone (5.1).
NOTE Commercially available columns with film thickness (d ) = 0,09 µm (for analysis up to C ) and
f 120
(d ) = 0,17 µm (for analysis up to C ) have been found to be satisfactory.
f 100
It is recommended that the column resolution, R, is at least 2 and not more than 4 (see B.2). Use some
form of column bleed compensation to obtain a stable baseline. This may be carried out by subtraction of
a column bleed profile previously obtained using exactly the same conditions as used for the sample
analysis, by injecting the same volume, using solvent for the blank run and sample dilution from one batch
taken at the same time, to avoid differences due to contamination.
6.3 Carrier gas control
The chromatograph shall be able to deliver a constant carrier gas flow over the whole temperature range
of the analysis.
6.4 Micro-syringe, of appropriate volume, e.g. 10 µl, for introduction of 1 µl of the calibration mixture
and test portions.
The micro-syringe may be operated either manually or automatically.
Plunger in needle syringes are not recommended due to excessive carry over of heavy ends to the
following analysis.
Table 2 — Typical operating conditions for gas chromatograph
PTV Injector COC Injector
Column length, m 5 5
Column internal diameter, mm 0,53 0,53
Column material Stainless steel Stainless steel
Stationary phase Methyl silicone Methyl silicone
Film thickness, µm 0,09 or 0,17 0,09 or 0,17
Initial column temperature, °C, Procedure A −20 −20
Initial column temperature, °C, Procedure B 40 40
Final column temperature, °C 430 430
Programme rate, °C/min 10 10
Hold time, min 5 5
Injector initial temperature, °C 100 ambient
Injector final temperature, °C 430 no setpoint
Programme rate, °C/min 15 15
Detector temperature, °C 430 430
Carrier gas He He
Carrier gas flow rate, ml/min 19 19
Sample size, µl 1,0 1,0
a a
Sample concentration, %(m/m) 2 % 2 %
a
See Clause 9.
6.5 Volumetric flask, 10 ml capacity.
6.6 Refrigerator, recommended to be of an explosion-protected design.
6.7 Analytical balance, able to weigh with a precision of 0,1 mg.
7 Sampling
Samples shall be taken as described in EN ISO 3170 or EN ISO 3171 (see the requirements of national
standards or regulations for the sampling of petroleum products for further information).
Store samples in either glass or metal containers. Plastic containers for sample storage shall not be used
as prolonged contact with the sample can cause contamination of the sample due to possible leaching of
the plasticizer.
8 Preparation of the apparatus
8.1 Gas chromatograph preparation
8.1.1 Set up and operate the gas chromatograph (6.1) in accordance with the manufacturer’s
instructions.
Typical operating conditions are shown in Table 2. For Procedure B, where the front end is determined
by a second analysis, the initial column temperature is higher than for Procedure A where a lower initial
column temperature is recommended to optimize the resolution of the front end and to minimize co-
elution of sample components with the solvent.
8.1.2 Deposits can form on the jet from combustion of decomposition products from the liquid
stationary phase. These will affect the characteristics of the detector and should be removed. However, if
poor results are still obtained, the jet should be replaced.
NOTE The following parameters are affected by deposits on the jet: increase in inlet pressure, FID difficult to
light, increase in the CS response and an off-specification reference oil.
To clean the jet, it is recommended that it is put in an ultrasonic cleaner with a suitable solvent, and a
cleaning wire used.
8.2 System performance check
Check the system performance at the intervals given and by the procedures specified in Annex C.
9 Corrected sample and reference material preparation
9.1 Mix the sample by shaking, warming prior to shaking where necessary.
9.2 Weigh approximately 0,1 g to 0,3 g, of the sample to the nearest 0,1 mg, into a clean 10 ml
volumetric flask (6.5) and add 5 ml to 7 ml carbon disulfide.
CAUTION — It is recommended that all work with carbon disulfide be carried out in an explosion
protected fume cupboard.
Shake the mixture to completely dissolve the test portion and then add carbon disulfide to the mark.
Immediately transfer the solution to auto test portion vials, seal, and store in a refrigerator until ready
for use.
If the density of the sample is known, the test portion may be prepared on a mass/mass basis, and the
following correction:
 
100 × m
 
(1)
ρ (mV/ )=
 
m /σ + m /σ
( ) ( )
11 22
 
where
ρ is the mass concentration in g/l;
m
is the mass of the test portion in grams;
m is the mass of carbon disulfide, in grams;
σ
is the density of the test portion at 20 °C, in kilograms per litre;
σ is the density of carbon disulfide at 20 °C, in kilograms per litre (= 1,26).
The density is quoted at 20 °C as a temperature approximately ambient in most laboratories. If the
laboratory temperature is outside 20 °C ± 5 °C, appropriate adjustments should be made.
Sample preparation is important to calculate the recovery of the sample. The sample may be prepared by
weighing the sample in a 10 ml flask as described. Using this procedure, it is not required to know or
measure the density of the sample. Due to the low boiling point and the health restrictions of CS it is
preferred to prepare the sample by weight and correct for the density.
NOTE When the density is unknown and therefore no correction can be applied, the error in the recovery
calculation is minor. Not correcting for density can result in a deviation of at most 1 % on the recovery for the
3 3
density range 700 kg/m to 1 000 kg/m .
10 Calibration
10.1 Carry out the steps given in 10.2 to 10.4 each day before sample analysis. The first run of the day
shall not be a blank, reference standard (5.9) or test portion, but it may be the calibration mixture (5.8).
10.2 Run the calibration mixture (5.8) using the specified procedure described in Clause 11.
NOTE Take care to ensure the test portion volume chosen does not allow any peak to exceed the linear range
of the detector or overload the column. A skew of > 3 indicates the sample is too concentrated and a skew of < 1
indicates an old column or dirty liner (see C.4). As a guide, 0,1 µl to 1 µl of the calibration mixture (5.8) has been
found to be suitable for columns with film thickness less than 0,17 µm.
10.3 Record the retention time of each component and plot the retention time versus the atmospheric
boiling point for each component to obtain the calibration curve.
NOTE The atmospheric boiling points of the alkanes are given in Annex E.
A typical chromatogram of the calibration mixture (5.8) is given in Figure 4 and a typical calibration curve
is given in Figure 5.
Key
X retention time (minutes)
Y signal
Figure 4 — Typical chromatogram of calibration mixture
10.4 Run the reference material (5.9) using the specified procedure in Clause 11. Calculate the boiling
range distribution of the reference material by the procedures specified in Annex A and compare this
with the consensus values for the reference material used.

Key
X temperature (°C)
Y retention time (minutes)
Figure 5 — Typical calibration curve (retention time vs. temperature)
11 Procedure
11.1 Run a solvent (blank) baseline analysis before the first sample analysis, and then after every five
samples. Subtract blank baselines from subsequent analyses (see Figure 6).
It is recommended to follow each test portion with a carbon disulfide blank to prevent carryover of heavy
non-volatile material into the next analysis.
11.2 Cool the column to the starting temperature and inject the selected sample volume.
11.3 Immediately start programming the column temperature upward at a rate that produces the
separation specified in Annex C.
11.4 Continue the run until the time for the highest component used for calibration has been exceeded.
11.5 For Procedure B: Run the DHA front end analysis.
NOTE A typical procedure for the DHA analysis is described in EN 15199-4 or IP 601 [5].
12 Visual inspection of the chromatograms
12.1 Blank run
The identification of a constant baseline at the end of the run is critical to the analysis of the reference
material. Constant attention shall be given to all factors that influence baseline stability, e.g. column
substrate bleed, septum bleed, detector temperature control, constancy of carrier gas flow, leaks and
instrument drift. The baseline at the end of each analysis shall merge with the baseline of the blank run
associated with it. Both signals shall merge to confirm integrity; if they do not, the analysis shall be
repeated (see Figure 6).
NOTE Users are encouraged to use in addition blank validation or rejection criteria proposed by simulated
distillation software.
a) good baseline b) bad baseline c) bad baseline
merging parallel crossing
Figure 6 — Baselines
12.2 Reference material
Using the data system, expand the chromatogram of the reference material, by 5 times. Merge the blank
baseline and observe the following points:
— the start of the area of interest is taken at a point on the baseline where the blank and the reference
material baselines are merged. This is taken before the start of the sample and after the end of the
solvent;
— the start of the elution of the reference sample is determined as given in A.5;
— the end of the area of interest is taken at a point on the baseline where the blank and the reference
material baselines are merged. This is taken after the end of the sample and at or before the end of
run;
— the end of the sample is determined as given in A.6;
— the reference material (5.9) has an IBP higher than 100°C and an FBP lower than 720°C, and therefore
the report of the reference material analysis must include an IBP and FBP result. When the data
system is not able to detect a start of the elution (A5), an end of the elution (A6), an IBP or FBP,
inspect the blank run (12.1).
12.3 Sample run
Using the data system, expand the chromatogram of the sample, by 5 times. Merge the blank baseline and
observe the following points:
— the start of the area of interest is taken at a point on the baseline where the blank and the sample
baselines are merged. This is taken before the start of the sample and after the end of the solvent;
— the start of the sample is determined as given in A.5;
— when the blank and sample baseline do not merge at the beginning of the chromatogram, no IBP can
be determined. The IBP is then reported as: lower than the boiling point of the first calibrated peak;
— the end of the area of interest is taken at a point on the baseline where the blank and the sample
baselines are merged. This is taken after the end of the sample and at or before the end of run;
— the end of the sample is determined as given in A.6;
— when the blank and sample baseline do not merge at the end of the chromatogram, no FBP can be
determined. The FBP is then reported as: higher than the boiling point of the last calibrated peak. In
this case the recovery is always lower than 100 %.
13 Calculation
Use the calculation protocol given in Annex A for the production of results.
For Procedure B, merge these results with the data from the DHA front end analysis using Annex D.
14 Expression of results
Report the tabulated results as follows:
a) report all temperatures to the nearest 1 °C;
b) report all percentages to the nearest 1 % (m/m);
c) report the 0,5 % (m/m) point as the initial boiling point, and the 99,5 % (m/m) point as the final
boiling point;
d) report intermediate percentages as required, at intervals of not less than 1 % (m/m).
15 Precision
15.1 General
The precision was determined by statistical examination of inter-laboratory test results using
EN ISO 4259:2006 [2] in a matrix of samples with properties in the range shown in Table 3.
NOTE A recalculation based on updated statistical techniques is pending and is to be shared with CEN.
15.2 Repeatability
The difference between two independent results obtained using this method for test material considered
to be the same in the same laboratory, by the same operator using the same equipment within short
intervals of time, in the normal and correct operation of the method that is expected to be exceeded with
a probability of 5 % due to random variation, conforms to the value given in Table 3.
15.3 Reproducibility
The difference between two independent results obtained using this method for test material considered
to be the same in different laboratories, where different laboratory means a different operator, different
equipment, different geographic location, and under different supervisory control, in the normal and
correct operation of the that is expected to be exceeded with a probability of 5 % due to random variation,
conforms to the value given in Table 3.
Table 3 — Precision values
Ranges
Recovered Repeatability (r) Reproducibility (R)
°C
% (m/m) °C °C Minimum Maximum
b
IBP 0,2 1,1 153
5 1,3 4,8 176 221
10 1,9 5,2 201 258
20 3,3 8,8 176 312
30 6,1 10 237 361
40 6,8 12 292 410
50 8,3 12 345 455
60 10 14 402 514
70 14 20 463 580
80 20 26 537 664
90 12 31 622 711
b
95 7,5 667 714
Ranges
Fractions Repeatability (r) Reproducibility (R)
%
°C % % Minimum Maximum
b b
200 0,3 1,5 3 23
250 0,4 2,5 9 31
300 0,5 3,0 18 40
350 0,6 3,4 28 50
400 0,7 3,7 38 58
450 0,9 4,1 49 66
Ranges
Fractions Repeatability (r) Reproducibility (R)
%
°C % % Minimum Minimum
500 1,0 4,3 58 74
550 1,1 4,5 63 80
600 1,2 3,9 66 85
650 1,3 4,1 68 89
700 1,2 4,1 69 92
750 1,3 4,2 87 93
b
No precision has been determined.

16 Test report
The test report shall specify:
a) reference to this document, i.e. EN 15199-3:2020;
b) the type and complete identification of the material tested;
c) the used method of sampling (see Clause 7), if known;
d) the result of the test (see Clause 14);
e) any deviation, by agreement or otherwise, from the standard procedures specified;
f) any unusual features observed;
g the date of the test.
Annex A
(normative)
Calculation procedure
A.1 Application
The algorithm given in this annex only applies for a slice width of 0,1 s to 0,2 s (10 Hz to 5 Hz). The
chromatogram for the reference material (5.9), the sample, and the baseline shall be set to zero. The
baseline chromatogram is subtracted from the Reference Material 5010 (5.9.2) and from the sample
chromatogram in order to obtain the net area.
NOTE An extended procedure is given as guidance in Annex B.
A.2 Starting conditions
The following data are required for the commencement of calculations:
a) sample data array (N data points);
b) reference material data array (N data points);
c) blank data array (N data points);
d) processed data file from calibration run with retention times of normal alkanes;
e) boiling points of normal alkanes used in calibration run (Annex E);
f) start sample time;
g) end sample time.
The data collection of the sample or reference should be identical to the data points used in the blank.
A.3 Zero sample or reference chromatogram
A.3.1 Subtract each blank slice area from the corresponding sample slice area.
A.3.2 Average the first twenty time slices from the subtracted slice areas.
A.3.3 Subtract the average slice area from each subtracted time slice to zero the chromatogram. Set
negative numbers to zero.
A.4 Sample area
Calculate the total sample area by summing each of the corrected area slices.
A.5 Start of sample elution time
By inspection of the chromatogram, select a start time for the area of interest, after the elution of the
solvent, where the baseline merges with the blank. The time slice, after this point, where the average rate
of change first exceeds 0,000 01 %/s of the total area is defined as the start of sample. Report this time
and/or indicate it on the chromatogram.
A.6 End of sample elution time
The end of the sample elution time is set by the user. It is the time equivalent to the temperature at which
the recovery is to be determined. This time shall be before the end of the temperature programme.
A.7 End of reference material elution time
By inspection of the chromatogram, select an end time of the area of interest where the baseline merges
with the blank. This shall be before the end of the temperature program. Calculate the average rate of
change per second between two consecutive time slices beginning with the last time slice and working
backwards in the manner given in A.5. Report this time and/or indicate it on the chromatogram. The end
of sample time can be set.
Determination of the start and end of sample elution time is done by slope detection. As the slope can
differ according to sample properties, the sensitivity levels may require adjustment, but this should not
be done during an analysis. Where possible, the use of set start and end of sample elution times is
recommended.
A.8 Corrected sample area
Calculate the total corrected sample area by summing the area slices from the start of sample to the end
of sample.
A.9 Normalization
A.9.1 Determine the area/weight factor for the reference material by summing all the area slices in the
external standard and dividing by the weight of the external standard taken in 10 ml carbon disulfide.
A.9.2 Determine the area/weight of the sample by summing all the area slices and dividing by the
weight of the sample taken in 10 ml carbon disulfide.
A.9.3 Determine the percentage recovery x by:
x= A //W××A W 100 (A.1)
( ) ( )
ss es es
where
A is the sum of the area slices of the sample determined in A.8;
s
W is the weight of sample taken in 10 ml carbon disulfide in A.9.2;
s
A is the sum of the area slices of the reference material determined in A.8;
es
W is the weight of the reference material taken in 10 ml carbon disulfide in A.9.1.
es
A.9.4 To convert time slices to area percent, start with the time slice corresponding to the start of the
sample and continue to the time slice corresponding to that set by the user and divide by the percentage
recovery determined in A.9.3.
A.10 Conversion of retention time to percent off
A.10.1 Initial boiling point
Starting with the time slice corresponding to start of sample, add the normalized area percents until the
total is equal to, or greater than, 0,5 %. Linearly interpolate to find the time corresponding to exactly
0,5 % of the total corrected sample area.
A.10.2 Intermediate boiling points
For each percent off between 1 % and 99 %, find the retention time where the cumulative area percent
is equal to or greater than the percent being determined. Use linear interpolation when the cumulative
sum exceeds the percent being determined.
A.10.3 Final boiling point
Find the retention time where the cumulative area percent is equal to, or greater than, 99,5 %. Use linear
interpolation to find the time corresponding to exactly 99,5 % of the total corrected sample area.
If the recovery at 720 °C or 750 °C (depending on the method used) is lower than 99,5 %, the FBP shall
be given as > 720 °C or > 750 °C at that recovery.
A.11 Conversion of retention times to boiling points
A.11.1 For each retention time determined in A.10.1 to A.10.3, find the pair of calibration retention times
that bracket the percent off time of interest.
A.11.2 Calculate each corresponding boiling point, B , in °C, from the following formula:
i
B − B
2 1
B ×−RR+ B (A.2)
( )
i i1 1
RR−
where
R is the retention time for 1 percent off;
i
R is the retention time of calibration point immediately below R ;
1 i
R is the retention time of calibration point immediately above R ;
2 i
B is the boiling point of compound at R ;
1 1
B is the boiling point of compound at R .
2 2
Report all results in accordance with Clause 14.

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