Petroleum products - Determination of boiling range distribution by gas chromatography method - Part 4: Light fractions of 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 ionization detection. The standard is applicable to stabilized crude oils and for the boiling range distribution and the recovery up to and including n-nonane. A stabilized crude oil is defined as having a Reid Vapour Pressure equivalent to or less than 82,7 kPa as determined by IP 481 [3].
NOTE   For the purposes of this European Standard, the terms “% (m/m)” and “% (V/V)” are used to represent respectively the mass fraction, ω, and the volume fraction, φ.
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 4: Leichte Fraktionen des Rohöls

Dieses Dokument beschreibt ein Verfahren zur Bestimmung des Siedeverlaufes von Mineralölerzeugnissen durch Kapillar-Gaschromatographie unter Anwendung der Flammenionisationsdetektion. Dieses Dokument ist anwendbar auf stabilisierte Rohöle und gilt für den Siedeverlauf und die Ausbeute bis einschließlich n-Nonan. Ein stabilisiertes Rohöl ist definiert, einen Reid-Dampfdruck von gleich oder kleiner als 82,7 kPa zu haben, bestimmt nach IP 481 [3].
Anhang C beschreibt einen Algorithmus zur Zusammenführung der mit diesem Verfahren erhaltenen Ergebnisse zur Siedepunktverteilung mit den Ergebnissen nach EN 15199-3. Dies führt zu einem Siedeverlauf und einer Ausbeute bis zu C120.
ANMERKUNG 1 Es gibt keine spezielle Präzisionsangabe für die nach EN 15199-3 und EN 15199-4 erhaltenen kombinierten Ergebnisse. Für die Präzision des Siedeverlaufs bis zu n-Nonan gelten die Präzisionsangaben von EN 15199-4. Für die Präzision des Siedeverlaufs von n-Nonan durch C120 gilt die Präzision von EN 15199-3.
ANMERKUNG 2 Für die Zwecke dieser Europäischen Norm wird zur Angabe des Massenanteils ω 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 dieses Dokuments, vor seiner Anwendung geeignete Maßnahmen für die Sicherheit und den Gesundheitsschutz des Personals zu ergreifen, und dafür Sorge zu tragen, dass behördliche und gesetzliche Maßnahmen eingehalten werden.

Produits pétroliers - Détermination de la répartition dans l'intervalle de distillation par méthode de chromatographie en phase gazeuse - Partie 4 : Fractions légères du pétrole brut

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. Le présent document s’applique aux pétroles bruts stabilisés pour déterminer la répartition dans l'intervalle de distillation ainsi que la récupération jusqu'au n-nonane inclus. Un pétrole brut stabilisé est défini comme ayant une pression de vapeur Reid équivalente à 82,7 kPa ou moins, telle que déterminée selon
l’IP 481 [3].
L'Annexe C présente un algorithme pour fusionner les résultats de la répartition des points d’ébullition obtenus en suivant cette méthode avec ceux obtenus selon l'EN 15199-3. Cela donne une répartition dans l’intervalle de distillation et une récupération jusqu'au C120.
NOTE 1   Il n'y a pas de données de fidélité spécifiques pour les résultats combinés obtenus après la fusion des résultats obtenus selon l'EN 15199-3 et ceux obtenus selon l'EN 15199-4. Pour la fidélité de la répartition dans l’intervalle de distillation jusqu'au n-nonane, les données de fidélité de l'EN 15199-4 s'appliquent. Pour la fidélité de la répartition dans l’intervalle de distillation du n-nonane au C120, la fidélité de l’EN 15199-3 s'applique.
NOTE 2   Pour les besoins de la présente Norme européenne, les termes “% (m/m)” et “% (V/V)” sont utilisés pour représenter respectivement la fraction massique, ω, et la fraction volumique, φ.
AVERTISSEMENT — L'utilisation du présent document peut impliquer la mise en œuvre de produits, d'opérations et d'équipements à caractère dangereux. Le présent document n'est pas censé aborder tous les problèmes de sécurité concernés par son usage. Il est de la responsabilité des utilisateurs du présent document de prendre les mesures appropriées pour assurer la sécurité et préserver la santé du personnel avant son application, et pour répondre aux exigences réglementaires et statutaires à cette fin.

Naftni proizvodi - Določanje porazdelitve območja vrelišč z metodo plinske kromatografije - 4. del: Lahke frakcije surovega olja

General Information

Status
Published
Public Enquiry End Date
29-Sep-2020
Publication Date
27-Oct-2021
Current Stage
6060 - National Implementation/Publication (Adopted Project)
Start Date
15-Sep-2021
Due Date
20-Nov-2021
Completion Date
28-Oct-2021

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Standards Content (sample)

SLOVENSKI STANDARD
SIST EN 15199-4:2021
01-december-2021
Nadomešča:
SIST EN 15199-4:2015
Naftni proizvodi - Določanje porazdelitve območja vrelišč z metodo plinske
kromatografije - 4. del: Lahke frakcije surovega olja

Petroleum products - Determination of boiling range distribution by gas chromatography

method - Part 4: Light fractions of crude oil

Mineralölerzeugnisse - Gaschromatographische Bestimmung des Siedeverlaufes - Teil 4:

Leichte Fraktionen des Rohöls

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

méthode de chromatographie en phase gazeuse - Partie 4 : Fractions légères du pétrole

brut
Ta slovenski standard je istoveten z: EN 15199-4:2021
ICS:
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
75.080 Naftni proizvodi na splošno Petroleum products in
general
SIST EN 15199-4:2021 en,fr,de

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

---------------------- Page: 1 ----------------------
SIST EN 15199-4:2021
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SIST EN 15199-4:2021
EN 15199-4
EUROPEAN STANDARD
NORME EUROPÉENNE
September 2021
EUROPÄISCHE NORM
ICS 75.080 Supersedes EN 15199-4:2015
English Version
Petroleum products - Determination of boiling range
distribution by gas chromatography method - Part 4: Light
fractions of crude oil

Produits pétroliers - Détermination de la répartition Mineralölerzeugnisse - Gaschromatographische

dans l'intervalle de distillation par méthode de Bestimmung des Siedeverlaufes - Teil 4: Leichte

chromatographie en phase gazeuse - Partie 4 : Fraktionen des Rohöls
Fractions légères du pétrole brut
This European Standard was approved by CEN on 14 June 2021.

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

© 2021 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 15199-4:2021 E

worldwide for CEN national Members.
---------------------- Page: 3 ----------------------
SIST EN 15199-4:2021
EN 15199-4:2021 (E)
Contents Page

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

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

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

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

4 Principle ................................................................................................................................................... 5

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

6 Apparatus ................................................................................................................................................ 5

6.1 Analytical balance capable of weighing to the nearest 0,1 mg ............................................. 5

6.2 Gas chromatograph .............................................................................................................................. 5

6.3 Detector .................................................................................................................................................... 6

6.4 Pre-column configurations ................................................................................................................ 7

6.4.1 Heated valve switching box (see Figure B.1) .............................................................................. 7

6.4.2 Injection port (see Figure B.2 and B.3) ......................................................................................... 7

6.5 Analytical column ................................................................................................................................. 7

6.5.1 General...................................................................................................................................................... 7

6.5.2 Resolution ................................................................................................................................................ 7

6.6 Skewness .................................................................................................................................................. 8

6.7 Data collection ....................................................................................................................................... 8

7 Sampling and sample handling ........................................................................................................ 9

8 Calculation of response factors ........................................................................................................ 9

9 Procedure .............................................................................................................................................. 10

9.1 Sample preparation ........................................................................................................................... 10

9.2 Determination of backflush time .................................................................................................. 10

9.2.1 Initial work ............................................................................................................................................ 10

9.2.2 Analytical column ............................................................................................................................... 10

9.2.3 Accelerated analytical column ....................................................................................................... 10

9.3 Sample analysis ................................................................................................................................... 11

9.3.1 Initial work ............................................................................................................................................ 11

9.3.2 Calculation of individual components results .......................................................................... 11

9.3.3 Boiling point distribution of fraction up to and including nonane ................................... 12

10 Reporting ............................................................................................................................................... 12

11 Precision ................................................................................................................................................ 12

11.1 General.................................................................................................................................................... 12

11.2 Repeatability, r .................................................................................................................................... 12

11.3 Reproducibility, R ............................................................................................................................... 12

12 Test report ............................................................................................................................................. 13

Annex A (informative) Analysis assistance ............................................................................................ 14

Annex B (informative) Apparatus configuration .................................................................................. 21

Annex C (normative) Algorithm for merging boiling point distribution results of EN 15199-3

and EN 15199-4 ................................................................................................................................... 23

Bibliography ....................................................................................................................................................... 31

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SIST EN 15199-4:2021
EN 15199-4:2021 (E)
European foreword

This document (EN 15199-4:2021) 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 March 2022, and conflicting national standards shall be

withdrawn at the latest by March 2022.

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 15199-4:2015.

In comparison with the previous edition, the following technical modification has been made.

The document is often used in combination with an analysis of boiling point distribution (Simdis) of crude

oil. Consensus has been reached about the algorithm for merging the results of the light end analysis and

the Simdis analysis. This algorithm is added as normative Annex C

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
Part 4 is harmonized with IP 601 [1] and ASTM D7900 [2].

Any feedback and questions on this document should be directed to the users’ national standards body.

A complete listing of these bodies can be found on the CEN website.

According to the CEN-CENELEC Internal Regulations, the national standards organisations of the

following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia,

Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland,

Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Republic of North

Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United

Kingdom.
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SIST EN 15199-4:2021
EN 15199-4:2021 (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. This document is applicable

to stabilized crude oils and for the boiling range distribution and the recovery up to and including

n-nonane. A stabilized crude oil is defined as having a Reid Vapour Pressure equivalent to or less than

82,7 kPa as determined by IP 481 [3].

Annex C specifies an algorithm for merging the boiling point distribution results obtained using this

method with the results obtained with EN 15199-3. This will result in a boiling range distribution and

recovery up to C120.

NOTE 1 There is no specific precision statement for the combined results obtained after merging the results of

EN 15199-3 and EN 15199-4. For the precision of the boiling range distribution up to n-nonane, the precision

statement of EN 15199-4 applies. For the precision of the boiling range distribution from n-nonane through C120,

the precision of EN 15199-3 applies.

NOTE 2 For the purposes of this document, the terms “% (m/m)” and “% (V/V)” are used to represent

respectively the mass fraction, ω, and the volume fraction, φ.

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 document to take appropriate measures to ensure safety and health of

personnel prior to application of the document and fulfil statutory and regulatory requirements for this

purpose.
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:

• IEC Electropedia: available at https://www.electropedia.org/
• ISO Online browsing platform: available at https://www.iso.org/obp
3.1
recovery

combined mass percentages of all light hydrocarbon identified in the chromatogram(except the internal

standard peak) of the sample up to and including n-nonane
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SIST EN 15199-4:2021
EN 15199-4:2021 (E)
4 Principle

An amount of internal standard is quantitatively added to an aliquot of the stabilized crude oil. A portion

of this mixture is injected into a pre-column in series via a splitter with a capillary analytical column.

When the n-nonane has quantitatively passed to the analytical column, the pre-column is back-flushed to

vent the higher boiling components. The individual components are identified by comparison with

reference chromatograms and a database of hydrocarbon compounds (see Annex A). The boiling point

distribution and recovery up to and including n-nonane (n-C9) is calculated.
5 Reagents and materials

5.1 Stationary phase for columns, with a bonded polydimethylsiloxane (PDMS) stationary phase for

both the pre-column and the analytical capillary column.
5.2 Compressed gases

5.2.1 Carrier gas, helium or hydrogen of at least 99,995 % (V/V) purity or higher is required. Any

oxygen present shall be removed by a suitable chemical filter.

CAUTION — If hydrogen is used as carrier gas, follow the safety instructions from the GC instrument

manufacturer.

5.2.2 Combustion gases, hydrogen and clean air for the flame ionization detector, and suitable filters

shall be used to ensure adequate gas cleanliness.

5.3 Internal standard, having a baseline resolution from any adjacent eluting peaks (Hexene-1 or

3,3-dimethyl-1-butene (99 % pure) have been found to be suitable).

5.4 Valve switching mixture, a qualitative mixture of approximately 1 % (m/m) of each normal alkane

from pentane to decane.
5.5 Carbon disulfide (CS ), purity 99,7 % (V/V) minimum.
WARNING — Extremely flammable and toxic by inhalation.
6 Apparatus
6.1 Analytical balance capable of weighing to the nearest 0,1 mg
6.2 Gas chromatograph

The typical operational characteristics of the gas chromatograph are described in Table 1.

Two different pre-column configurations are possible.

The first configuration (A) employs a 1 metre column contained in a temperature controlled valve box,

separately controlled. The valve box in this configuration is isothermal (see Annex B).

The second configuration (B) is a short pre-column (a packed injection port liner), that fits into the

injection port. The injection port will be temperature programmed (see Annex B).
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SIST EN 15199-4:2021
EN 15199-4:2021 (E)
6.3 Detector

Flame Ionization Detector with sufficient sensitivity to detect 1 % mass n-heptane with a peak height of

at least 10 % full-scale deflection under the conditions given in the method. When operating at this

sensitivity level, detector stability shall be such that a baseline drift of not more than 1 % per hour is

obtained. The detector shall be connected to the column carefully to avoid any cold spots. The detector

shall be capable of operating at a temperature equivalent to the maximum column temperature used.

Table 1 —Typical chromatographic conditions
Pre- Pre- Analytical Accelerated
column column
Analytical
A B
Column length – m 1,0 0,075 50 or 100 40
Column internal diameter –
2 2,5 0,25 0,10
Column material polydimethylsiloxane
Phase loading – % 5 10
Film thickness – µm 0,5
Injection volume – µL 0,1 0,1
Injector split ratio 100 : 1 600 : 1
Injector temperature – °C 300 100
Pre-column temperature –
200 100
Injector program rate –
50
°C/min
Final injector temperature –
300
Initial oven temperature –
35 35
Hold time – min 30 2,6
50 → 45 °C
Oven program rate –°C/min 2
(hold time 3 min)
5 → 60 °C
(hold time 3 min)
9,5 → 200 °C
200
200
Final oven temperature – °C
(hold time
(hold time 1 min)
20 min)
Flame Ionization Detector –
300 300
---------------------- Page: 8 ----------------------
SIST EN 15199-4:2021
EN 15199-4:2021 (E)
6.4 Pre-column configurations
6.4.1 Heated valve switching box (see Figure B.1)

For the isothermal 1 metre pre-column, a heated valve box is needed with its own temperature control.

The box will contain an automated six-port valve which is used to back-flush the pre-column.

The six-port valve should be made out of material which will not be corroded by the sample (some crude

oils contain high amounts of sulfur components). The valve shall be situated in a heated isothermal oven

and be attached to the injector, pre-column, splitter, analytical column and the detector without any cold

spots.
6.4.2 Injection port (see Figure B.2 and B.3)

A temperature programmable injection port capable of containing a 7,5 cm pre-column, and this injection

port shall be equipped with a back-flush option. This injector can be connected directly to the capillary

column (Figure B.2) or via a splitter (Figure B.3).
6.5 Analytical column
6.5.1 General

The column elutes hydrocarbons in a boiling point order. The eluate from the injector passes through the

pre-column before eluting onto the analytical column.
6.5.2 Resolution

Determine the resolution between the internal standard and the nearest n-paraffin peak as per

Formula (1).
2 tt−
( )
2 1
(1)
1,699 w + w
( )
where
P is the column resolution;
t is the retention time of the first peak (peak 1, see Figure 1);
t is the retention time of the second peak (peak 2, see Figure 1);
w is the peak width at half height of peak 1;
w is the peak width at half height of peak 2.

With Hexene-1 as I.S., the resolution is determined between the I.S and n-hexane. The resolution shall be

at least 2,0.
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SIST EN 15199-4:2021
EN 15199-4:2021 (E)
Figure 1 — Determination of resolution
6.6 Skewness

Determine the skew of the n-hexane peak by measuring the width of the leading part of the peak at 5 %

peak height (A) and the width of the following part of the peak at 5 % peak height (B). The ratio (B)/(A)

shall be not less than 1 or more than 4. See Figure 2 for further clarification.
Figure 2 —Calculation of peak skewness
6.7 Data collection

A PC based chromatography data system or integrator with suitable software can be used. For systems

using the analytical column, a data -sampling rate of 5 Hz is the recommended minimum.

For systems using the accelerated analytical column, a data-sampling rate of 20 Hz is required.

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SIST EN 15199-4:2021
EN 15199-4:2021 (E)
7 Sampling and sample handling
Take samples in accordance with either EN ISO 3170 or EN ISO 3171.
8 Calculation of response factors

Calculate the flame ionization detector response factor relative to methane, which is considered to have

a response factor of unity (= 1), for each hydrocarbon group type of a particular carbon number using

Formula (2).
 
C ×+C H × H × 0,748 7
( ) ( )
aw n aw n
 
RRf = (2)
C × C
( )
aw n
where

RRf is relative response factor for a hydrocarbon type group of a particular carbon number;

C is atomic mass of carbon, 12,011;

C is number of carbon atoms in the hydrocarbon type group, of a particular carbon

number;
H is atomic mass of hydrogen, 1,008,

H is number of hydrogen atoms in the hydrocarbon type group of a particular carbon

number, and 0,748 7 is factor to normalize the result to a methane response of unity

(= 1).
Table 2 gives some response factors already calculated.
Table 2 — Calculated response factors for hydrocarbons
No. of Carbon Naphthenes Paraffins Cyclic olefins Mono-olefins Aromatics
atoms
3 0,916 0,874
4 0,906 0,874
5 0,874 0,899 0,849 0,874
6 0,874 0,895 0,853 0,874 0,811
7 0,874 0,892 0,856 0,874 0,820
8 0,874 0,890 0,859 0,874 0,827
9 0,874 0,888 0,860 0,874 0,832
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SIST EN 15199-4:2021
EN 15199-4:2021 (E)
9 Procedure
9.1 Sample preparation

Weigh to the nearest 0,1 mg, approximately 5 g ± 0,2 g of sample into a tared, screw-capped vial.

Add approximately 0,15 g ± 0,02 g of internal standard and reweigh to the nearest 0,1 mg. Where the

mass of available sample is less than 5 g, the internal standard shall be added to create the equivalent of

a 3 % concentration.

Gently mix the two liquids without causing the sample to degas. Carbon disulfide (5.5) can be added to

improve the viscosity of the sample.

Fill the sample into GC vials with a minimum amount of headspace. Store the vials in a sub ambient

cupboard until use.

NOTE The amount of sample and internal standard taken can vary according to the level of Iight-end

components in the sample and the amount of the sample available.
9.2 Determination of backflush time
9.2.1 Initial work

With the pre-column and analytical column in series, inject an aliquot of the pre-column switch test

mixture (5.4) and determine the ratio of the alkanes.
9.2.2 Analytical column

Set the switching time to 1 min and repeat the analysis. Increase or decrease the valve time to ensure the

complete recovery of the highest alkane required (e.g. nonane) and partly recovery of the next alkane

(e.g. decane). (See 9.3.1 and the example chromatogram in Figure 3).
9.2.3 Accelerated analytical column

Set the switching time to 30 s and repeat the analysis. Increase or decrease the valve time to ensure the

recovery of the highest alkane required (e.g. nonane) and partly recovery of the next alkane (e.g. decane).

(For assistance in the identification of individual components see [1] and [2] and example chromatogram

(Figure 3)).
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SIST EN 15199-4:2021
EN 15199-4:2021 (E)
Key
1 n-Pentane 3 n-Heptane 5 n-Nonane
2 n-Hexane 4 n-Octane 6 n-Decane
Figure 3 — Example chromatogram showing elution for determining backflush time
9.3 Sample analysis
9.3.1 Initial work

Inject a suitable aliquot of the sample and internal standard onto the inlet of the pre-column which is in

series with the analytical column. At the time determined above (9.2) switch the valve and back-flush the

high boilers to vent.

The valve time reflects the highest carbon number required. As a general rule, if zC is required, then

(z+1)C should be eluted.
9.3.2 Calculation of individual components results

Calculate each of the individual hydrocarbons up to and including n-nonane the mass fraction ω using

Formula (3):
A ⋅ RRf
ω ×ω (3)
Q IS
A ⋅ RRf
IS IS
where

RRf and RRf are the relative response factors relative to methane respectively for

Q IS
component Q and the internal standard IS as calculated in Clause 8;
A and A
are the areas resulting from the integration of the chromatographic detector
Q IS
signal within the specified retention time interval for component Q and for the
internal standard IS, respectively; and
ω is the mass fraction (in %) of the internal standard.

These generic response factors can be transformed when using an internal standard (in this case a C

olefin for which the response relative to methane is 0,874) to specific factors belonging to this internal

standard, by dividing all the generic factors by 0,874.
---------------------- Page: 13 ----------------------
SIST EN 15199-4:2021
EN 15199-4:2021 (E)

By summation of all the mass percentages per peak up to and including nonane, the mass percent of this

fraction shall be calculated.
See EN 15199-3 [4] for merging of the results to give a full crude analysis.
9.3.3 Boiling point distribution of fraction up to and including nonane

Plot for all the hydrocarbons (beginning with the lowest boiling point) the cumulative mass percent

versus the boiling point up to the last peak of interest, e.g. n-nonane.
10 Reporting

Report the cumulative mass percent versus boiling point results to the nearest 0,01 % (m/m), and 0,5 °C

respectively, up to the last peak of interest, e.g. n -nonane.
11 Precision
11.1 General

The precision of this test method was determined by statistical evaluation of the interlaboratory test

results consisting of 14 laboratories (10 from Europe and 4 from the USA) analysing 8 crude oil samples

in duplicate. The repeatability and reproducibility were calculated following the procedures of

EN ISO 4259 [5]. The full details of the round robin are in [6].
11.2 Repeatability, r

The difference between two test results, obtained by the same operator with the same apparatus under

constant operating conditions on identical test material would in the long run, in the normal and correct

operation of the test method, exceed the following value in absolute value in only one case in twenty:

rX0,019 82(+ 8) (4)
where
X is the average of the two results being compared, in % (m/m).
11.3 Reproducibility, R

The difference between two single and independent test results, obtained by different operators working

in different laboratories on identical test material, would in the long run, in the normal and correct

operation of the test method, exceed the following value in only one case in twenty:

RX0,126 7(+ 8) (5)
where
X is the average of the two results being compared, in % (m/m).
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12 Test report
The test report shall specify at least:
a) The document used (including its year of publication);
b) type and complete identification of the material tested;
c) result of the test (see Clause 10);

d) any unusual features observed, by agreement or otherwise, from the standard procedures specified;

e) the date of the test.
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Annex A
(informative)
Analysis assistance

This Annex presents examples of retention index data and chromatogram for identifying individual

components. Table A.1 encompasses the total analysis, i.e. the detailed hydrocarbon analysis up to

n-nonane.
Table A.1 — Example report of an analysis
Component name
Time Retention Mass Peak area
(min) index % (pA.s)
2,729 200 ethane 0,018 5 2,097
2,878 300 propane 0,311 1 36,079
3,111 355,5 i-butane 0,246 4 28,907
3,312 400 n-butane 0,848 4 99,544
3,413 410,2 2,2-dimethylpropane 0,005 7 0,678
3,475 416,3 - 0,000 9 0,107
3,680 435,7 - 0,001 5 0,179
4,051 468,1 i-pentane 0,762 2 90,048
4,452 500 n-pentane 1,060 4 125,278
4,832 516 - 0,001 3 0,154
5,080 525,7 CS2 0 42,838
5,219 531 2,2-dimethylbutane 0,029 3 3,474
5,824 552,3 - 0,001 0 0,121
6,021 558,8 cyclopentane 0,143 6 17,454
6,068 560,3 2,3-dimethylbutane 0,078 6 9,328
6,198 564,5 2-methylpentane 0,546 3 64,793
6,720 580,2 3-methylpentane 0,336 1 39,861
6,945 586,6 hexene-1 0 603,992
7,333 597,2 - 0,002 4 0,282
7,439 600 n-hexane 1,015 6 120,461
7,652 604 - 0,002 7 0,317
7,930 609 - 0,002 5 0,301
8,448 617,8 - 0,002 0 0,237
8,695 621,9 2,2-dimethylpentane 0,024 1 2,872
8,824 623,9 methylcyclopentane 0,593 8 72,154
9,057 627,6 2,4-dimethylpentane 0,054 5 6,496
9,390 632,7 2,2,3-trimethylbutane 0,005 0 0,595
10,313 645,8 benzene 0,252 2 33,01
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Time Retention Component name Mass Peak area
(min) index % (pA.s)
10,764 651,8 3,3-dimethylpentane 0,015 3 1,82
11,021 655,1 cyclohexane 0,832 3 101,143
11,809 664,8 2-meth
...

SLOVENSKI STANDARD
oSIST prEN 15199-4:2020
01-september-2020
Naftni proizvodi - Določevanje porazdelitve območja vrelišč z metodo plinske
kromatografije - 4. del: Lahke frakcije surovega olja

Petroleum products - Determination of boiling range distribution by gas chromatography

method - Part 4: Light fractions of crude oil

Mineralölerzeugnisse - Gaschromatographische Bestimmung des Siedeverlaufes - Teil

4: Leichte Fraktionen des Rohöls

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

méthode de chromatographie en phase gazeuse - Partie 4 : Fractions légères du pétrole

brut
Ta slovenski standard je istoveten z: prEN 15199-4
ICS:
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
75.080 Naftni proizvodi na splošno Petroleum products in
general
oSIST prEN 15199-4:2020 en

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

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oSIST prEN 15199-4:2020
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oSIST prEN 15199-4:2020
DRAFT
EUROPEAN STANDARD
prEN 15199-4
NORME EUROPÉENNE
EUROPÄISCHE NORM
July 2020
ICS 75.080 Will supersede EN 15199-4:2015
English Version
Petroleum products - Determination of boiling range
distribution by gas chromatography method - Part 4: Light
fractions of crude oil

Produits pétroliers - Détermination de la répartition Mineralölerzeugnisse - Gaschromatographische

dans l'intervalle de distillation par méthode de Bestimmung des Siedeverlaufes - Teil 4: Leichte

chromatographie en phase gazeuse - Partie 4 : Fraktionen des Rohöls
Fractions légères du pétrole brut

This draft European Standard is submitted to CEN members for enquiry. It has been drawn up by the Technical Committee

CEN/TC 19.

If this draft becomes a European Standard, 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.

This draft European Standard was established by CEN 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.

Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are

aware and to provide supporting documentation.

Warning : This document is not a European Standard. It is distributed for review and comments. It is subject to change without

notice and shall not be referred to as a European Standard.
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. prEN 15199-4:2020 E

worldwide for CEN national Members.
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Contents Page

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

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

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

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

4 Principle ............................................................................................................................................................. 5

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

6 Apparatus .......................................................................................................................................................... 5

6.1 Analytical balance ........................................................................................................................................... 5

6.2 Gas chromatograph ........................................................................................................................................ 5

6.3 Detector .............................................................................................................................................................. 5

6.4 Pre-column configurations .......................................................................................................................... 7

6.5 Analytical column ........................................................................................................................................... 7

6.6 Skewness ............................................................................................................................................................ 8

6.7 Data collection ................................................................................................................................................. 8

7 Sampling and sample handling .................................................................................................................. 8

8 Calculation of response factors .................................................................................................................. 9

9 Procedure .......................................................................................................................................................... 9

9.1 Sample preparation ....................................................................................................................................... 9

9.2 Determination of backflush time ............................................................................................................ 10

9.3 Sample analysis ............................................................................................................................................. 10

10 Reporting ......................................................................................................................................................... 11

11 Precision .......................................................................................................................................................... 11

11.1 General.............................................................................................................................................................. 11

11.2 Repeatability, r .............................................................................................................................................. 12

11.3 Reproducibility, R ......................................................................................................................................... 12

12 Test report ....................................................................................................................................................... 12

Annex A (informative) Analysis assistance ...................................................................................................... 13

Annex B (informative) Apparatus configuration ............................................................................................ 20

Annex C (normative) Algorith for merging boiling point distribution results of EN 15199-3

and EN 15199-4 ............................................................................................................................................. 22

C.1 Introduction .................................................................................................................................................... 22

C.2 Summary of the procedure ........................................................................................................................ 22

C.3 Elements required to perform merge of EN 15199-4 and EN 15199-3 at the merge

point ................................................................................................................................................................... 23

C.4 Data merging procedure ............................................................................................................................ 25

C.5 Reporting merged results .......................................................................................................................... 26

C.6 Normalizing results for recoveries in excess of 100 % by mass after merging...................... 29

Bibliography ................................................................................................................................................................. 30

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European foreword

This document (prEN 15199-4:2020) 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 document is currently submitted to the CEN Enquiry.
This document will supersede EN 15199-4:2015.

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 part of the standard is based on IP 601 [1] and describes the determination of boiling range

distribution of hydrocarbons up to n-nonane in crude oil. The results of this test method can be

combined with those from EN 15199-3, to give a full boiling point distribution of crude oil.

Part 4 is harmonized with IP 601 [1] and ASTM D7900 [2].

In comparison with the previous edition, the following technical modifications have been made. The

document is often used in combination with an analysis of boiling point distribution (Simdis) of crude

oil. Consensus has been reached about the algorithm for merging the results of the light end analysis

and the Simdis analysis. This algorithm is added as informative Annex C.
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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. This document is applicable

to stabilized crude oils and for the boiling range distribution and the recovery up to and including n-

nonane. A stabilized crude oil is defined as having a Reid Vapour Pressure equivalent to or less than

82,7 kPa as determined by IP 481 [3].

Annex C describes an algorithm for merging the boiling point distribution results obtained using this

method with the results obtained with EN 15199-3. This will result in a boiling range distribution and

recovery up to C120.

NOTE 1 There is no specific precision statement for the combined results obtained after merging the results of

EN 15199-3 and EN 15199-4, For the precision of the boiling range distribution up to n-nonane, the precision

statement of EN 15199-4 applies. For the precision of the boiling range distribution from n-nonane through C120,

the precision of EN 15199-3 applies.

NOTE 2 For the purposes of this European Standard, the terms “% (m/m)” and “% (V/V)” are used to represent

respectively the mass fraction, ω, and the volume fraction, φ.

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 document to take appropriate measures to ensure safety and health of

personnel prior to application of the document and fulfil statutory and regulatory requirements for this

purpose.
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:

• IEC Electropedia: available at http://www.electropedia.org/
• ISO Online browsing platform: available at http://www.iso.org/obp
3.1
recovery

combined mass percentages of all light hydrocarbon peaks (except the internal standard peak) in the

sample up to and including n-nonane
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4 Principle

An amount of internal standard is quantitatively added to an aliquot of the stabilized crude oil. A

portion of this mixture is injected into a pre-column in series via a splitter with a capillary analytical

column. When the n-nonane has quantitatively passed to the analytical column, the pre-column is back-

flushed to vent the higher boiling components. The individual components are identified by comparison

with reference chromatograms and a database of hydrocarbon compounds (see Annex A). The boiling

point distribution and recovery up to and including n-nonane (n-C9) is calculated.

5 Reagents and materials

5.1 Stationary phase for columns, with a bonded polydimethylsiloxane (PDMS) stationary phase for

both the pre-column and the analytical capillary column.
5.2 Compressed gases

5.2.1 Carrier gas, helium or hydrogen of at least 99,995 % (V/V) purity or higher is required. Any

oxygen present shall be removed by a suitable chemical filter.

CAUTION — If hydrogen is used as carrier gas, follow the safety instructions from the GC instrument

manufacturer.

5.2.2 Combustion gases, hydrogen and clean air for the flame ionization detector, and suitable filters

shall be used to ensure adequate gas cleanliness.

5.3 Internal standard, having a baseline resolution from any adjacent eluting peaks (Hexene-1 or

3,3-dimethylbutene-1 (99 % pure) have been found to be suitable).

5.4 Valve switching mixture, a qualitative mixture of approximately 1 % (m/m) of each normal

alkane from pentane to decane.
5.5 Carbon disulphide (CS ), purity 99,7 % (V/V) minimum.
WARNING — Extremely flammable and toxic by inhalation.
6 Apparatus
6.1 Analytical balance
Capable of weighing with an accuracy of 0,1 mg.
6.2 Gas chromatograph

The typical operational characteristics of the gas chromatograph are described in Table 1.

Two different pre-column configurations are possible:

The first configuration (A) employs a 1-m column contained in a temperature controlled valve box,

separately controlled. The valve box in this configuration is isothermal.

The second configuration (B) is a short pre-column (a packed injection port liner), that fits into the

injection port. The injection port will be temperature programmed.
6.3 Detector

Flame Ionization Detector with sufficient sensitivity to detect 1 % mass n-heptane with a peak height of

at least 10 % full-scale deflection under the conditions given in the method. When operating at this

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sensitivity level, detector stability shall be such that a baseline drift of not more than 1 % per hour is

obtained. The detector shall be connected to the column carefully to avoid any cold spots. The detector

shall be capable of operating at a temperature equivalent to the maximum column temperature used.

Table 1 —Typical chromatographic conditions
Pre-column Pre-column Analytical Accelerated
A B
Analytical
Column length – m 1,0 0,075 50 or 100 40
Column internal diameter –
2 2,5 0,25 0,10
Column material polydimethylsiloxane
Phase loading – % 5 10
Film thickness – µm 0,5
Injection volume – µL 0,1 0,1
Injector split ratio 100:1 600:1
Injector temperature – °C 300 100
Pre-column temperature – °C 200 100
Injector program rate –
50
°C/min
Final injector temperature – °C 300
Initial oven temperature – °C 35 35
Hold time – min 30 2,6
50 → 45 °C
Oven program rate –°C/min 2
(hold time 3 min)
5 → 60 °C
(hold time 3 min)
9,5 → 200 °C
200
200
Final oven temperature – °C (hold time
(hold time 1 min)
20 min)
Flame Ionization Detector – °C 300 300
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6.4 Pre-column configurations
6.4.1 Heated valve switching box (see Figure B.1)

For the isothermal 1 metre pre-column, a heated valve box is needed with its own temperature control.

The box will contain an automated six-port valve which is used to back-flush the pre-column.

The six-port valve should be made out of material which will not be corroded by the sample (Some

crude oils contain high amounts of sulfur components). The valve shall be situated in a heated

isothermal oven and be attached to the injector, pre-column, splitter, analytical column and the detector

without any cold spots.
6.4.2 Injection port (see Figure B.2 and B.3)

A temperature programmable injection port capable of containing a 7,5 cm pre-column, and this

injection port shall be equipped with a back-flush option. This injector may be connected directly to the

capillary column (Figure B.2) or via a splitter (Figure B.3).
6.5 Analytical column
6.5.1 General

The column elutes hydrocarbons in a boiling point order. The eluate from the injector passes through

the pre-column before eluting onto the analytical column.
6.5.2 Resolution

Determine the resolution between the internal standard and the nearest n-paraffin peak as per

Formula (1).
2 tt−
( )
2 1
(1)
1,699 w + w
( )
Where
P is the column resolution;
t is the retention time of the first peak (peak 1, see Figure 1);
t is the retention time of the second peak (peak 2, see Figure 1);
wl is the peak width at half height of peak 1;
w is the peak width at half height of peak 2.

With Hexene-1 as I.S., the resolution is determined between the I.S and n-hexane. The resolution shall

be at least 2,0.
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Figure 1 — Determination of resolution
6.6 Skewness

Determine the skew of the n-hexane peak by measuring the width of the leading part of the peak at 5 %

peak height (A) and the width of the following part of the peak at 5 % peak height (B). The ratio (B)/(A)

shall be not less than 1 or more than 4. See Figure 2 for further clarification.
Figure 2 —Calculation of peak skewness
6.7 Data collection

A PC based chromatography data system or integrator with suitable software may be used. For systems

using the analytical column, a data -sampling rate of 5 Hz is the recommended minimum.

For systems using the accelerated analytical column, a data-sampling rate of 20 Hz is required.

7 Sampling and sample handling
Take samples in accordance with either EN ISO 3170 or EN ISO 3171.
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8 Calculation of response factors

Calculate the flame ionization detector response factor relative to methane, which is considered to have

a response factor of unity (= 1), for each hydrocarbon group type of a particular carbon number using

Formula (2).
 
C ×+C H × H × 0,748 7
( ) ( )
aw n aw n
 
R = (2)
C × C
( )
aw n
Where

R is relative response factor for a hydrocarbon type group of a particular carbon number,

C is atomic mass of carbon, 12,011,

C is number of carbon atoms in the hydrocarbon type group, of a particular carbon number,

H is atomic mass of hydrogen, 1,008,

H is number of hydrogen atoms in the hydrocarbon type group of a particular carbon number,

and 0,748 7 is factor to normalize the result to a methane response of unity (= 1).

Table 2 gives some response factors already calculated.
Table 2 — Calculated response factors for hydrocarbons
No. of Carbon Naphthenes Paraffins Cyclic olefins Mono-olefins Aromatics
atoms
3 0,916 0,874
4 0,906 0,874
5 0,874 0,899 0,849 0,874
6 0,874 0,895 0,853 0,874 0,811
7 0,874 0,892 0,856 0,874 0,820
8 0,874 0,890 0,859 0,874 0,827
9 0,874 0,888 0,860 0,874 0,832
9 Procedure
9.1 Sample preparation

Weigh to the nearest 0,1 mg, approximately 5 g ± 0,2 g of sample into a tared, screw-capped vial.

Add approximately 0,15 g ± 0,02 g of internal standard and reweigh to the nearest 0,1 mg. Where the

mass of available sample is less than 10 g, the internal standard shall be added to create the equivalent

of a 3 % concentration.

Gently mix the two liquids without causing the sample to degas. Carbon disulphide (5.5) may be added

to improve the viscosity of the sample.

Fill the sample into GC vials with a minimum amount of headspace. Store the vials in a sub ambient

cupboard until use.

NOTE The amount of sample and internal standard taken can vary according to the level of Iight-end

components in the sample and the amount of the sample available.
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9.2 Determination of backflush time
9.2.1 Initial work

With the pre-column and analytical column in series, inject an aliquot of the pre-column switch test

mixture (5.4) and determine the ratio of the alkanes.
9.2.2 Analytical column

Set the switching time to 1 min and repeat the analysis. Increase or decrease the valve time to ensure

the complete recovery of the highest alkane required (e.g. nonane) and partly recovery of the next

alkane (e.g. decane). (See 9.3.1 and the example chromatogram in Figure 3)
9.2.3 Accelerated analytical column

Set the switching time to 30 s and repeat the analysis. Increase or decrease the valve time to ensure the

recovery of the highest alkane required (e.g. nonane) and partly recovery of the next alkane (e.g.

decane). (For assistance in the identification of individual components see [1] and [2] and example

chromatogram (Figure 3)).
Key
1 n-Pentane 3 n-Heptane 5 n-Nonane
2 n-Hexane 4 n-Octane 6 n-Decane
Figure 3 — Example chromatogram showing elution for determining backflush time
9.3 Sample analysis
9.3.1 Initial work

Inject a suitable aliquot of the sample and internal standard onto the inlet of the pre-column which is in

series with the analytical column. At the time determined above (9.2) switch the valve and back-flush

the high boilers to vent.

The valve time reflects the highest carbon number required. As a general rule, if zC is required, then

(z+1)C should be eluted.
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9.3.2 Calculation of individual components results

Calculate each of the individual hydrocarbons up to and including n-nonane the mass fraction ω using

Formula (3):
A ⋅ Rf
ωω× (3)
Q IS
A ⋅ Rf
IS IS
Where

RfQ and RfIS are the relative response factors relative to methane respectively for

component Q and the internal standard IS as calculated in Clause 8,

A and A are the areas resulting from the integration of the chromatographic detector

Q IS
signal within the specified retention time interval for component Q and for the
internal standard IS, respectively, and
ω is the mass fraction (in %) of the internal standard.

These generic response factors may be transformed when using an internal standard (in this case a C

olefin for which the response relative to methane is 0,874) to specific factors belonging to this internal

standard, by dividing all the generic factors by 0,874.

By summation of all the mass percentages per peak up to and including nonane, the mass percent of this

fraction shall be calculated.

NOTE See EN 15199-3 [4] for merging of the results to give a full crude analysis.

9.3.3 Boiling point distribution of fraction up to and including nonane

Plot for all the peaks (beginning with the lowest boiling point) the cumulative mass percent versus the

boiling point up to the last peak of interest, e.g. n-nonane.
10 Reporting

Report the cumulative mass percent versus boiling point results to the nearest 0,01 % (m/m), and

0,5° C respectively, up to the last peak of interest, e.g. n-nonane.
11 Precision
11.1 General

The precision of this test method was determined by statistical evaluation of the interlaboratory test

results consisting of 14 laboratories (10 from Europe and 4 from the USA) analysing 8 crude oil samples

in duplicate. The repeatability and reproducibility were calculated following the procedures of

EN ISO 4259 [5]. The full details of the round robin are in [6].
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11.2 Repeatability, r

The difference between two test results, obtained by the same operator with the same apparatus under

constant operating conditions on identical test material would in the long run, in the normal and correct

operation of the test method, exceed the following value in absolute value in only one case in twenty:

rX0,019 82+ 8 (4)
( )
Where
X is the average of the two results being compared, in % (m/m).
11.3 Reproducibility, R

The difference between two single and independent test results, obtained by different operators

working in different laboratories on identical test material, would in the long run, in the normal and

correct operation of the test method, exceed the following value in only one case in twenty:

RX0,126 7+ 8 (5)
( )
Where
X is the average of the two results being compared, in % (m/m).
12 Test report
The test report shall specify:
a) reference to this document, i.e. EN 15199-4;
b) type and complete identification of the material tested;
c) result of the test (see Clause 10);

d) any deviation, by agreement or otherwise, from the standard procedures specified;

e) date of the test.
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Annex A
(informative)
Analysis assistance

This annex presents examples of retention index data and chromatogram for identifying individual

components. Table A.1 encompasses the total analysis, i.e. the detailed hydrocarbon analysis up to n-

nonane.
Table A.1 — Example report of an analysis
Time Retention Component name Mass % Peak area
(min) index (pA.s)
2,729 200 ethane 0,018 5 2,097
2,878 300 propane 0,311 1 36,079
3,111 355,5 i-butane 0,246 4 28,907
3,312 400 n-butane 0,848 4 99,544
3,413 410,2 2,2-dimethylpropane 0,005 7 0,678
3,475 416,3 - 0,000 9 0,107
3,680 435,7 - 0,001 5 0,179
4,051 468,1 i-pentane 0,762 2 90,048
4,452 500 n-pentane 1,060 4 125,278
4,832 516 - 0,001 3 0,154
5,080 525,7 CS2 0 42,838
5,219 531 2,2-dimethylbutane 0,029 3 3,474
5,824 552,3 - 0,001 0 0,121
6,021 558,8 cyclopentane 0,143 6 17,454
6,068 560,3 2,3-dimethylbutane 0,078 6 9,328
6,198 564,5 2-methylpentane 0,546 3 64,793
6,720 580,2 3-methylpentane 0,336 1 39,861
6,945 586,6 hexene-1 0 603,992
7,333 597,2 - 0,002 4 0,282
7,439 600 n-hexane 1,015 6 120,461
7,652 604 - 0,002 7 0,317
7,930 609 - 0,002 5 0,301
8,448 617,8 - 0,002 0 0,237
8,695 621,9 2,2-dimethylpentane 0,024 1 2,872
8,824 623,9 methylcyclopentane 0,593 8 72,154
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Time Retention Component name Mass % Peak area
(min) index (pA.s)
9,057 627,6 2,4-dimethylpentane 0,054 5 6,496
9,390 632,7 2,2,3-trimethylbutane 0,005 0 0,595
10,313 645,8 benzene 0,252 2 33,01
10,764 651,8 3,3-dimethylpentane 0,015 3 1,82
11,021 655,1 cyclohexane 0,832 3 101,143
11,809 664,8 2-methylhexane 0,330 5 39,357
11,940 666,4 2,3-dimethylpentane 0,127 8 15,217
12,157 668,9 1,1-dimethylcyclopentane 0,088 7 10,774
12,584 673,7 3-methylhexane 0,376 9 448,89
13,146 679,9 1c,3-dimethylcyclopentane 0,158 4 19,243
13,418 682,7 1t,3-dimethylcyclopentane 0,146 2 17,771
13,581 684,4 3-ethylpentane 0,034 1 4,056
13,689 685,6 1t,2-dimethylcyclopentane 0,263 3 31,989
15,165 699,9 n-heptane 1,005 6 119,756
methylcyclohexane+1c,2-
17,487 717,5 dimethylcyclopentane 1,568 5 190,596
2,2-dimethylhexane+1,1,3-
17,992 721 trimethylcyclopentane 0,094 3 11,257
19,214 729 2,2,3-trimethylpentane 0,114 2 13,632
19,614 731,6 2,5-dimethylhexane+2,2,3-trimethylpentane 0,051 9 6,189
19,889 733,3 2,4-dimethylhexane 0,069 7 8,323
20,653 737,9 1,trans
...

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