SIST EN 15199-1:2021

Petroleum products - Determination of boiling range distribution by gas chromatography method - Part 1: Middle distillates and lubricating base oils

This European Standard specifies a method for the determination of the boiling range distribution of petroleum products by capillary gas chromatography using flame ionisation detection. The standard is applicable to materials having a vapour pressure low enough to permit sampling at ambient temperature and a boiling range of at least 100 °C. The standard is applicable to distillates with initial boiling points (IBP) above 100 °C and final boiling points (FBP) below 750 °C, for example, middle distillates and lubricating base stocks.
The test method is not applicable for the analysis of petroleum or petroleum products containing low molecular weight components (for example naphthas, reformates, gasolines, diesel). Components containing hetero atoms (for example alcohols, ethers, acids, or esters) or residue are not to be analyzed by this test method.
NOTE   For the purposes of this European Standard, the terms “% (m/m)” and “% (V/V)” are used to represent respectively the mass fraction and the volume fraction.
WARNING — The use of this European Standard may involve hazardous materials, operations and equipment. This European Standard 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 1: Mitteldestillate und Grundöle

Dieses Dokument legt ein Verfahren zur Bestimmung des Siedeverlaufes in Mineralölerzeugnissen mit Hilfe der Kapillar-Gaschromatographie mit einem Flammenionisationsdetektor (FID) fest. Die Norm ist anwendbar auf Mineralölerzeugnisse mit einem für die Probenahme bei Umgebungstemperatur ausreichend niedrigen Dampfdruck und mit einem Siedebereich von mindestens 100 °C. Die Norm ist anwendbar auf Destillate mit einem Siedebeginn (IBP) oberhalb von 100 °C und mit einem Siedeende (FBP) unterhalb von 750 °C, wie z. B. Mitteldestillate und Grundöle.
Das Prüfverfahren ist nicht anzuwenden für die Analyse von Mineralöl oder Mineralölerzeugnissen mit niedermolekularen Anteilen (z. B. Naphtha, Reformat, Ottokraftstoff) oder Mitteldestillaten, wie z. B. Diesel- und Flug-(turbinen-)kraftstoff.
Mineralöl oder Mineralölerzeugnisse, die Blendkomponenten mit Heteroatomen enthalten (z. B. Alkohole, Ether, Säuren oder Ester), oder Rückstände sind mit diesem Prüfverfahren nicht zu untersuchen.
ANMERKUNG Für die Zwecke dieses Dokuments wird zur Angabe des Massenanteils einer Substanz der Ausdruck „% (m/m)“ und für den Volumenanteil 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 in Hinblick auf

Produits pétroliers - Détermination de la répartition dans l'intervalle de distillation par méthode de chromatographie en phase gazeuse - Partie 1: Distillats moyens et huiles lubrifiantes

Le présent document spécifie une méthode de détermination de la répartition dans l’intervalle de distillation des produits pétroliers par chromatographie en phase gazeuse capillaire avec une détection par ionisation de flamme. Il s’applique aux produits dont la pression de vapeur est suffisamment faible pour permettre l’échantillonnage à la température ambiante et dont l’intervalle de distillation est d’au moins 100 °C. Le présent document s’applique aux distillats dont le point d’ébullition initial (IBP) est supérieur à 100 °C et le point d’ébullition final (FBP) est inférieur à 750 °C, par exemple, les distillats moyens et les huiles lubrifiantes.
La méthode d’essai ne s’applique pas pour l’analyse de pétrole ou de produits pétroliers ayant des composants de faible masse moléculaire (par exemple les naphtas, réformats, essences et distillats moyens comme le gazole et le carburéacteur). Les composants contenant des hétero-atomes (par exemple alcools, éthers, acides ou esters) ou les résidus ne peuvent pas être analysés suivant cette méthode.
NOTE Pour les besoins du présent document, les termes "% (m/m)" et "% (V/V)" sont utilisés pour représenter respectivement la fraction massique et la fraction volumique.
AVERTISSEMENT - L’utilisation du présent document peut impliquer 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 de consulter et 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 - 1. del: Srednji destilati in mazalna olja

General Information

• Status: Published
• Public Enquiry End Date: 02-Jan-2020
• Publication Date: 26-Jan-2021
• ICS: 75.080 - Petroleum products in general
• ICS: 75.100 - Lubricants, industrial oils and related products
• 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 15199-1:2020 - Petroleum products - Determination of boiling range distribution by gas chromatography method - Part 1: Middle distillates and lubricating base oils

Relations

• Replaces: SIST EN 15199-1:2006 - Petroleum products - Determination of boiling range distribution by gas chromatography method - Part 1: Middle distillates and lubricating base oils
• Effective Date: 01-Mar-2021

Standards Content (Sample)

SLOVENSKI STANDARD
SIST EN 15199-1:2021
01-marec-2021
Nadomešča:
SIST EN 15199-1:2006
Naftni proizvodi - Določanje porazdelitve območja vrelišč z metodo plinske
kromatografije - 1. del: Srednji destilati in mazalna olja

Petroleum products - Determination of boiling range distribution by gas chromatography

method - Part 1: Middle distillates and lubricating base oils

Mineralölerzeugnisse - Gaschromatographische Bestimmung des Siedeverlaufes - Teil 1:

Mitteldestillate und Grundöle

Produits pétroliers - Détermination de la répartition dans l'intervalle de distillation par

méthode de chromatographie en phase gazeuse - Partie 1: Distillats moyens et huiles

lubrifiantes
Ta slovenski standard je istoveten z: EN 15199-1:2020
ICS:
75.080 Naftni proizvodi na splošno Petroleum products in
general
75.100 Maziva Lubricants, industrial oils and
related products
SIST EN 15199-1:2021 en,fr,de

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

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SIST EN 15199-1:2021
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SIST EN 15199-1:2021
EN 15199-1
EUROPEAN STANDARD
NORME EUROPÉENNE
December 2020
EUROPÄISCHE NORM
ICS 75.080 Supersedes EN 15199-1:2006
English Version
Petroleum products - Determination of boiling range
distribution by gas chromatography method - Part 1:
Middle distillates and lubricating base oils

Produits pétroliers - Détermination de la répartition Mineralölerzeugnisse - Gaschromatographische

dans l'intervalle de distillation par méthode de Bestimmung des Siedeverlaufes - Teil 1:

chromatographie en phase gazeuse - Partie 1 : Distillats Mitteldestillate und Grundöle

moyens et huiles lubrifiantes
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 15199-1:2020 E

worldwide for CEN national Members.
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SIST EN 15199-1:2021
EN 15199-1:2020 (E)
Contents Page

European foreword ....................................................................................................................................................... 3

1 Scope .................................................................................................................................................................... 4

2 Normative references .................................................................................................................................... 4

3 Terms and definitions ................................................................................................................................... 4

4 Principle ............................................................................................................................................................. 6

5 Reagents and materials ................................................................................................................................. 6

6 Apparatus ........................................................................................................................................................... 9

7 Sampling .......................................................................................................................................................... 11

8 Preparation of the apparatus .................................................................................................................. 11

8.1 Gas chromatograph preparation ............................................................................................................ 11

8.2 System performance check ....................................................................................................................... 11

9 Sample preparation ..................................................................................................................................... 11

10 Calibration ...................................................................................................................................................... 11

11 Procedure........................................................................................................................................................ 13

12 Visual inspection of the chromatograms ............................................................................................. 14

13 Calculation ...................................................................................................................................................... 14

14 Expression of results ................................................................................................................................... 14

15 Precision .......................................................................................................................................................... 14

15.1 General ............................................................................................................................................................. 14

15.2 Repeatability .................................................................................................................................................. 15

15.3 Reproducibility ............................................................................................................................................. 15

16 Test report ...................................................................................................................................................... 16

Annex A (normative) Calculation procedure .................................................................................................. 17

Annex B (normative) System performance check ......................................................................................... 22

Annex C (normative) Boiling points of n-alkanes .......................................................................................... 24

Bibliography ................................................................................................................................................................. 26

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SIST EN 15199-1:2021
EN 15199-1:2020 (E)
European foreword

This document (EN 15199-1:2020) 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 15199-1:2006.
The main changes in this edition are:
— the precision is extended for the recovery points between 10 % and 50 %;

— the text has been updated editorially in order to give better guidance to operators executing the

test.

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 fractions of crude oil.

This document specifies the determination of boiling range distribution of materials with initial boiling

points (IBP) above 100 °C and final boiling points (FBP) below 750 °C. For testing materials with initial

boiling points (IBP) above 100 °C and final boiling point (FBP) above 750 °C, Part 2 of the standard can

be used. For testing materials with initial boiling points (IBP) below 100 °C and final boiling points

(FBP) above 750 °C, such as crude oils, Part 3 can be used. Part 4 describes the determination of boiling

range distribution of hydrocarbons up to n-nonane in crude oil.

This document is based on IP Test Method IP 480 [4] and ASTM Test Method ASTM D6352 [3].

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.
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SIST EN 15199-1:2021
EN 15199-1:2020 (E)
1 Scope

This document specifies 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 materials having a vapour pressure low enough to permit sampling at ambient temperature and a

boiling range of at least 100 °C. The standard is applicable to distillates with initial boiling points (IBP)

above 100 °C and final boiling points (FBP) below 750 °C, for example, middle distillates and lubricating

base stocks.

The test method is not applicable for the analysis of petroleum or petroleum products containing low

molecular weight components (for example naphtha’s, reformates, gasolines) or middle distillates like

Diesel and Jet fuel.

Petroleum or petroleum products containing blending components which contain heteroatoms (for

example alcohols, ethers, acids, or esters) or residue are not to be analysed by this test method.

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

respectively the mass fraction and the volume fraction.

WARNING — The use of this document can 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 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:

— ISO Online browsing platform: available at https://www.iso.org/obp
— IEC Electropedia: available at http://www.electropedia.org/
3.1
initial boiling point
IBP

temperature corresponding to the retention time at which a net area counts equal to 0,5 % of the total

sample area (3.6) under the chromatogram is obtained (see Figure 1)
3.2
final boiling point
FBP

temperature corresponding to the retention time at which a net area (3.7) counts equal to 99,5 % of the

total sample area (3.6) under the chromatogram is obtained (see Figure 1)
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EN 15199-1:2020 (E)
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
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
Key
1 start of elution 4 end of elution
2 IBP (3.1) X retention time (minutes)
3 FBP (3.2) Y Response (pA)
Figure 1 — Typical chromatogram
3.7
net area

cumulative area counts for the sample minus the cumulative area count for the blank

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EN 15199-1:2020 (E)
3.8
recovery

ratio of the cumulative area count 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

A test portion is introduced into a gas chromatographic column, which separates hydrocarbons in the

order of increasing boiling point. The column temperature is raised at a linear reproducible rate and the

area under the chromatogram is recorded throughout the analysis. Boiling points are assigned to the

time-axis from a calibration curve obtained by running a mixture of known n-alkanes, covering the

sample boiling range, under the same conditions. From these data, the boiling range distribution is

obtained.

Several SIMDIS methods are standardized test methods and each one is dedicated to a certain boiling

point range or product.

EN ISO 3924 [1] is limited to products having an initial boiling point greater than 55 °C, a final boiling

point lower than 538 °C and having a vapour pressure sufficiently low to permit sampling at ambient

temperature.

EN 15199-2 is applicable to materials with initial boiling points (IBP) above 100 °C and final boiling

points (FBP) above 750 °C, for example, heavy distillate fuels and residuals. The method is not

applicable to bituminous samples.

EN 15199-3 is applicable to crude oils. The boiling range distribution and recovery (3.8) up to C or

100
C can be determined.
120
5 Reagents and materials

Unless otherwise stated, only chemicals of recognized analytical quality shall be used.

5.1 Carrier gas, helium, of at least 99,999 % (V/V) purity. Any oxygen present is removed by a

chemical resin filter.
WARNING — Follow the safety instructions from the filter supplier.
5.2 Hydrogen, grade suitable for flame ionization detectors.
5.3 Compressed air, suitable for flame ionization detectors.

5.4 Alkanes, n-alkanes of at least 98 % (m/m) purity from C to C , C , C , C , C , C , C and

5 10 12 14 16 18 20 24
C .
NOTE The calibration mixture from EN ISO 3924 [1] is also suitable.
5.5 Polywax 655® or 1000®
5.6 Carbon disulfide, (CS ) purity 99,7 % (V/V) minimum.
WARNING — Extremely flammable and toxic by inhalation.

CAUTION — It is recommended that all work with CS is carried out in an explosion protected fume

cupboard.
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EN 15199-1:2020 (E)

Cyclohexane (C H )—(>99 % pure) can be used in place of CS for the preparation of the calibration

6 12 2

mixture. However, the precision of this method is based on calibration mixtures, reference material and

samples prepared with CS only.
5.7 Calibration mixture

Dissolve 0,1 g of Polywax (5.5) in 7 ml CS (5.6), warming gently if necessary. Prepare an equal volume

mixture of alkanes (5.4) 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 of the C peak, and

retention time versus boiling point calibration curve.
5.8 Reference materials
5.8.1 A reference material has two functions:

— External Standard: to determine the recovery of samples by comparing the total sample area (3.6)

of the reference material with the total sample area (3.5) of the unknown sample;

— 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. A typical example is given in

(5.8.2).

5.8.2 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.

5.8.3 Binary gravimetric blend, a binary distillate mixture with boiling points ranges that gives a

baseline at the start, a baseline between the two peaks and an end time that is as close to the end of the

chromatogram as possible (see Figure 2 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.

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EN 15199-1:2020 (E)
Table 1 — Reference Material 5010
Accepted
% Allowable difference
Reference
Recovery 95,5 % Confidence Interval
value
°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
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Key
Y response (pA)
X retention time (minutes)
Figure 2 — 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 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.

6.1.2 Column temperature programmer, capable of linear programmed temperature operation over

a range of 10 °C above ambient to 450 °C.

6.1.3 Sample inlet system, consisting of a programmable temperature vaporizer (PTV) or cold on-

column (COC) injection port. The maximum temperature of the injection device shall be equal to, or

higher than, the final oven temperature. The minimum temperature shall be low enough to prevent

sample or solvent flashback, but high enough to allow sample focusing at the front of the column.

Table 2 contains the typical operating conditions.
6.2 Column

6.2.1 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.

6.2.2 Use a metal column, 0,53 µm internal diameter coated with methyl silicone. Commercially

available columns with film thickness (d ) = 0,09 µm (for analysis up to C ) and (d ) = 0,17 µm (for

f 120 f
analysis up to C ) have been found to be satisfactory.
100

It is recommended that the column resolution, R, is at least 2 and not more than 4 (see B.2).

6.2.3 Use some form of column bleed compensation to obtain a stable baseline. This can 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.

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SIST EN 15199-1:2021
EN 15199-1:2020 (E)
Table 2 — Typical operating conditions for gas chromatograph
Unit Specification
Column length m 5
Column internal diameter mm 0,53
Column material — Ultimetal
Stationary phase — Methyl silicone
Film thickness µm 0,09 or 0,17
Initial column temperature °C 35
Final column temperature °C 430
Program rate °C/min 10
Injector initial temperature °C 100
Injector final temperature °C 430
Program rate °C/min 15
Hold time min 5
Detector temperature °C 450
Detector hydrogen flow (5.2) ml/min 35
Detector air flow (5.3) ml/min 350
Carrier gas — Helium
Carrier gas flow rate ml/min 19
Sample size µl 1,0
Sample concentration % (m/m) 2
Injector — PTV or COC

A carrier gas flow rate up to 25 ml/min can be used to ensure all material elutes before the

end of the temperature program.
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. 5 µl, for introduction of 1 µl of the calibration mixture

and test portions. Plunger in needle syringes are not recommended due to excessive carry over of heavy

ends to the following analysis.
6.5 Volumetric flask, 10 ml capacity.
6.6 Refrigerator, shall be of an explosion-protected design.
6.7 Analytical balance, capable of weighing to the nearest 0,1 mg.
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EN 15199-1:2020 (E)
7 Sampling

Samples shall be taken as specified 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.

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.

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 material. To clean the jet, an ultrasonic

cleaner with a suitable solvent, and a cleaning wire can be used.
8.2 System performance check

Check the system performance at the intervals given and by the procedures specified in Annex B.

9 Sample preparation

Make a mass concentration of 2 % to 3 % solution of the sample in CS (5.6). Transfer to an autosampler

vial and immediately cap.
10 Calibration

10.1 It is highly recommended to 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, a reference material or a sample, due to the

possible elution of extraneous components, which have built up in the injector, but it may be the

calibration mixture (5.7).
10.2 Run the calibration mixture (5.7) as specified in Clause 11.

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. Determine the skewness according to Annex B System

Performance (B4). A skew of > 3 indicates the sample is too concentrated and a skew of < 1 indicates an

old column or dirty liner. As a guide, 1 µl of the calibration mixture (5.7) 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 (5.4 and 5.5) are given in Annex C.

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EN 15199-1:2020 (E)

A typical chromatogram of the calibration mixture (5.7) is given in Figure 3 and a typical calibration

curve is given in Figure 4.
Key
Y response (pA)
X retention time (minutes)
Figure 3 — Typical chromatogram of calibration mixture
Key
Y retention time (minutes)
X temperature °C
Figure 4 — Typical calibration curve
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EN 15199-1:2020 (E)

10.4 Run the Reference Material 5010 (5.8.2) 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.

If the results are not within the specified range, it is advised to carefully follow the manufacturer’s

instructions regarding chromatographic problem solving and related diagnostics.
11 Procedure

11.1 Run a solvent (blank) baseline analysis before the first sample analysis, and then after every five

samples. Using the data system, merge the blank baselines and the subsequent analyses and observe the

last part of the chromatogram. The baseline shall look like example a in Figure 5.

a) good baseline b) bad baseline c) bad baseline
merging parallel crossing
(high FBP) (Low FBP)
Figure 5 — Baselines

The peak shape of the CS and the identification of a constant baseline at the end of the run is critical to

the analysis. Constant attention shall be given to all factors that influence the peak shape and the

baseline stability, e.g. column substrate bleed, septum bleed, detector temperature control, constancy of

carrier gas (5.1) flow, leaks and instrument drift. The peak shape of the CS is influenced by the

cleanliness of the liner and or the connection between the column and the liner (Figure 6). 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.

NOTE Users are encouraged to use in addition blank validation or rejection criteria proposed by simulated

distillation software.
Key
A good
B bad
Figure 6 — Solvent Peak Shape

11.2 Run the calibration and the reference sample according to Clause 10 under the same analysis

circumstances, see Table 2.

11.3 Verify the system performance check as specified in Annex B, and when they passed the criteria,

the system is ready for sample analysis.
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11.4 It is recommended to repeat the calibration and or the reference sample at the end of the sample

analysis sequence to monitor the instruments performance during the sequence.
12 Visual inspection of the chromatograms

Using the data system, expand the chromatogram of the reference or 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 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 start of the sample is determined as given in A.5.
The end of the sample is determined as given in A.6.
13 Calculation

Use the calculation protocol given in Annex A for the calculation of the results.

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 (3.1), and the 99,5 % (m/m) point as the

final boiling point (3.2);

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 4259:1995 [2] in a matrix of samples with properties in the range shown in Table 3.

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Table 3 — Range of results
Boiling range Range of results
% (m/m) °C
IBP 283 to 467
5 311 to 507
10 322 to 521
20 336 to 540
30 348 to 555
40 359 to 568
50 369 to 582
60 379 to
...