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

This European Standard describes 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 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.
NOTE 1   This 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 determine the applicability of regulatory limitations.
NOTE 2   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 : 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 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
Current Stage
6060 - National Implementation/Publication (Adopted Project)
Start Date
06-Jan-2021
Due Date
13-Mar-2021
Completion Date
27-Jan-2021

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SLOVENSKI STANDARD
SIST EN 15199-3:2021
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
SIST EN 15199-3:2021 en,fr,de

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

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SIST EN 15199-3:2021
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SIST EN 15199-3:2021
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.
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SIST EN 15199-3:2021
EN 15199-3:2020 (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 ...................................................................................................................... 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

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SIST EN 15199-3:2021
EN 15199-3:2020 (E)
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.
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SIST EN 15199-3:2021
EN 15199-3:2020 (E)
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.
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SIST EN 15199-3:2021
EN 15199-3:2020 (E)
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
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SIST EN 15199-3:2021
EN 15199-3:2020 (E)
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.
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SIST EN 15199-3:2021
EN 15199-3:2020 (E)
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).
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SIST EN 15199-3:2021
EN 15199-3:2020 (E)

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.
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SIST EN 15199-3:2021
EN 15199-3:2020 (E)
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
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SIST EN 15199-3:2021
EN 15199-3:2020 (E)
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.
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SIST EN 15199-3:2021
EN 15199-3:2020 (E)
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 %
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.
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SIST EN 15199-3:2021
EN 15199-3:2020 (E)
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:
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SIST EN 15199-3:2021
EN 15199-3:2020 (E)
 
100 × m
 
(1)
ρ (mV/ )=
 
m /σ + m /σ
( ) ( )
11 22
 
where
ρ is the mass concentration in g/l;
is the mass of the test portion in grams;
m is the mass of carbon disulfide, in grams;
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
...

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