BRITISH STANDARD BS EN

15199-2:2006
BS 2000-507:
2006

Petroleum products —
Determination of
boiling range
distribution by gas
chromatography
method —
Part 2: Heavy distillates and residual
fuels

The European Standard EN 15199-2:2006 has the status of a

British Standard

ICS 75.080

12&23<,1*:,7+287%6,3(50,66,21(;&(37$63(50,77('%<&23<5,*+7/$:
BS EN 15199-2:2006

National foreword

This British Standard was published by BSI. It is the UK implementation of

EN 15199-2:2006.
The UK participation in its preparation was entrusted to Technical Committee
PTI/13, Petroleum testing and terminology.
A list of organizations represented on PTI/13 can be obtained on request to its
secretary.
Energy Institute, under the brand of IP, publishes and sells all Parts of
BS 2000, and all BS EN petroleum test methods that would be Part of BS 2000,
both in its annual publication “Standard methods for analysis and testing of
petroleum and related products and British Standard 2000 Parts” and
individually.
Further information is available from:
Energy Institute, 61 New Cavendish Street, London W1G 7AR.
Tel: 020 7467 7100. Fax: 020 7255 1472.
This publication does not purport to include all the necessary provisions of a
contract. Users are responsible for its correct application.
Compliance with a British Standard cannot confer immunity from
legal obligations.

This British Standard was Amendments issued since publication

published under the authority
of the Standards Policy and
Strategy Committee Amd. No. Date Comments
on 31 January 2007

© BSI and Energy Institute 2007

ISBN 978 0 580 50181 4

EUROPEAN STANDARD EN 15199-2
NORME EUROPÉENNE
EUROPÄISCHE NORM October 2006

ICS 75.080

English Version

Petroleum products - Determination of boiling range distribution

by gas chromatography method - Part 2: Heavy distillates and
residual fuels

Produits pétroliers - Détermination de la répartition dans Mineralölerzeugnisse - Gaschromatographische

l'intervalle de distillation par méthode chromatographie en Bestimmung des Siedeverlaufes - Teil 2: Schweröle und
phase gazeuse - Partie 2: Distillats severes et residuals Rückstandsöle

This European Standard was approved by CEN on 28 August 2006.

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 Central Secretariat 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 Central Secretariat has the same status as the official
versions.

CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,
Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania,
Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.

EUROPEAN COMMITTEE FOR STANDARDIZATION

COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG

Management Centre: rue de Stassart, 36 B-1050 Brussels

© 2006 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 15199-2:2006: E
worldwide for CEN national Members.
EN 15199-2:2006 (E)

Contents Page

Foreword..............................................................................................................................................................3
1 Scope ......................................................................................................................................................4
2 Normative references ............................................................................................................................4
3 Terms and definitions ...........................................................................................................................4
4 Principle..................................................................................................................................................6
5 Reagents and materials ........................................................................................................................6
6 Apparatus ...............................................................................................................................................9
7 Sampling procedure ............................................................................................................................10
8 Preparation of the apparatus..............................................................................................................10
8.1 Gas chromatograph preparation........................................................................................................10
8.2 System performance check ................................................................................................................10
9 Sample and reference material preparation......................................................................................10
10 Calibration ............................................................................................................................................11
11 Procedure .............................................................................................................................................13
12 Visual inspection of the chromatograms ..........................................................................................13
13 Calculation............................................................................................................................................14
14 Expression of results ..........................................................................................................................14
15 Precision...............................................................................................................................................14
15.1 General..................................................................................................................................................14
15.2 Repeatability.........................................................................................................................................14
15.3 Reproducibility.....................................................................................................................................14
16 Test report ............................................................................................................................................15
Annex A (normative) Calculation procedure ..................................................................................................16
Annex B (normative) System performance check .........................................................................................19
Annex C (informative) Boiling points of normal alkanes ..............................................................................21
Annex D (informative) Additional guidance for the calculation algorithm ..................................................22
Bibliography ......................................................................................................................................................26

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 EN 15199-2:2006 (E)

Foreword
This document (EN 15199-2:2006) 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 April 2007, and conflicting national standards shall be withdrawn at the latest by
April 2007.

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

This part of the standard describes the determination of boiling range distribution of materials with initial boiling
points (IBP) above 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) below 100 °C and final boiling points (FBP) above 750 °C, such as
crude oils, Part 3 is applicable.

This part of the standard is a joint development between the EI [1], ASTM [2] and CEN.

According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Republic, Denmark,
Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta,
Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United
Kingdom.

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EN 15199-2:2006 (E)

1 Scope
This European Standard specifies a method for the determination of the boiling range distribution of petroleum
products by capillary gas chromatography using flame ionisation detection. The standard is applicable to
materials having a vapour pressure low enough to permit sampling at ambient temperature, and which have a
boiling range of at least 100 °C. The standard is applicable to materials with initial boiling points (IBP) above
100 °C and final boiling points (FBP) above 750 °C, for example, heavy distillate fuels and residuals. The
method is not applicable to bituminous samples.

The test method is not applicable for the analysis of petroleum or petroleum products containing low molecular
weight components (for example naphthas, reformates, gasolines, diesel). Components containing hetero
atoms (for example alcohols, ethers, acids, or esters) or residue are not to be analyzed by this test method.

NOTE For the purposes of this European Standard, the terms “% (m/m)” and “% (V/V)” are used to represent
respectively the mass fraction and the volume fraction.

WARNING — The use of this European Standard may involve hazardous materials, operations and
equipment. This European Standard does not purport to address all of the safety problems associated
with its use. It is the responsibility of the user of this standard to establish appropriate safety and
health practices and to determine the applicability of regulatory limitations prior to use.

2 Normative references
The following referenced documents are indispensable for the application 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 3170:2004)

EN ISO 3171, Petroleum liquids — Automatic pipeline sampling (ISO 3171:1988)

3 Terms and definitions

For the purposes of this document, the following terms and definitions apply.

NOTE Explanation of some of the terms is given in Figure 1.

3.1
initial boiling point
IBP
temperature corresponding to the retention time at which a net area count equal to 0,5 % of the total sample
area under the chromatogram is obtained

3.2
final boiling point
FBP
temperature corresponding to the retention time at which a net area count equal to 99,5 % of the total sample
area under the chromatogram is obtained

3.3
area slice
area resulting from the integration of the chromatographic detector signal within a specified retention time
interval

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 EN 15199-2:2006 (E)

NOTE 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.

Key:

1 start of elution 3 final boiling point (FBP)

2 initial boiling point (IBP) 4 end of elution

Figure 1 — Typical chromatogram

3.4
corrected area slice
area slice corrected for baseline offset by subtraction of the exactly corresponding area slice in a previously
recorded blank (non-sample) analysis

3.5
cumulative corrected area
accumulated sum of corrected area slices from the beginning of the analysis through a given retention time,
ignoring any non-sample area for example of solvent

3.6
slice rate
time interval used to integrate the continuous (analogue) chromatographic detector response during an
analysis

NOTE The slice rate is expressed in Hz (for example integrations per second or slices per second).

3.7
slice time
analysis time associated with each area slice throughout the chromatographic analysis

NOTE The slice time is the time at the end of each contiguous area slice.

3.8
total sample area
cumulative corrected area, from the initial area point to the final area point, where the chromatographic signal
has returned to baseline after complete sample elution

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EN 15199-2:2006 (E)

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 count of the sample to that of the reference material (external standard) corrected
for dilution and material weights combined with the percentage of light ends, if applicable

4 Principle
A test portion is introduced into a gas chromatographic column, which separates hydrocarbons in the order of
increasing boiling point. The column temperature is raised at a linear reproducible rate and the area under the
chromatogram is recorded throughout the analysis. Boiling points are assigned to the time-axis from a
calibration curve, which is obtained by running a mixture of known normal alkanes covering the test portion
boiling range, under the same conditions. From these data, the boiling range distribution is obtained. The
recovery at a specified temperature is determined by comparing the area under the chromatogram with that of
a reference standard which has been completely eluted. The temperature at which the recovery was
measured is recorded.

NOTE If the found recovery is less than 100 %, the final boiling point is reported as 720 °C or 750 °C at that recovery.

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, of at least 99,999 % (V/V) purity. Any oxygen present is
removed by a chemical resin filter.

Warning Follow the safety instructions from the filter supplier.

5.3 Hydrogen, grade suitable for flame ionisation detectors.

5.4 Compressed air, regulated for flame ionisation detectors.

5.5 Alkanes, normal alkanes of at least 98 % (m/m) purity from C5 to C10, C12, C14, C16, C18, C20, C24 and C28
to be used with Polywax 655 or 1000 (5.6).

NOTE The calibration mixture from ISO 3924 [3] is also suitable.

5.6 Polywax 655 or 1000

5.7 Carbon disulfide, with a minimum purity of 99,7 % (V/V).

WARNING — Extremely flammable and toxic.

NOTE 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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 EN 15199-2:2006 (E)

Key:

/ good
X bad

Figure 2 — Solvent peak shape

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 of the C20 peak, and retention time
versus boiling point calibration curve.

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.

 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 analyzed by laboratories participating in
the test method cooperative study. Consensus values for the boiling range distribution of this sample are
given in Table 1.

5.9.3 Cyclohexane. (C6H12)—(99+ % pure) may be used in place of CS2 for the preparation of the
calibration mixture.

5.9.4 Binary gravimetric blend, a binary distillate mixture with boiling points ranges that gives a baseline
at the start, a baseline between the two peaks and an end time that is as close to the end of the
chromatogram as possible (see Figure 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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EN 15199-2:2006 (E)

Key:

A response
B retention time (min)

Figure 3 — Typical chromatogram of binary gravimetric blend distillate

Table 1 — Reference Material 5010

% recovered Reference Maximum

temperature allowable range
°C 95,5 % CI
°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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 EN 15199-2:2006 (E)

6 Apparatus
6.1 Gas chromatograph, with the following performance characteristics.

6.1.1 Flame ionisation 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.

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

6.1.3 Sample inlet system, consisting of a programmable temperature vaporizer (PTV) or cold on-column
(COC) injection port. The maximum temperature of the injection device shall be equal to, or higher than, the
final oven temperature. The minimum temperature shall be low enough to prevent sample or solvent flashback,
but high enough to allow sample focusing at the front of the column. Table 2 contains the typical operating
conditions.

6.2 Column

Use a metal column with 0,53 mm internal diameter and coated with methyl silicone (5.1). Commercially
available columns with film thickness (df) = 0,09 µm (for analysis up to C120) and (df) = 0,17 µm (for analysis up
to C100) have been found to be satisfactory.

NOTE 1 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.

NOTE 2 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.

Table 2 — Typical operating conditions for gas chromatograph

Column length, m 5
Column internal diameter, mm 0,53
Column material Ultimetal
Stationary phase Methyl silicone
Film thickness, µm 0,09 or 0,17
Initial column temperature, °C 35
Final column temperature, °C 430
Program rate, °C/min 10
Injector initial temperature, °C 100
Injector final temperature, °C 430
Program rate, °C/min 15
Hold time, min 5
Detector temperature, °C 450
Carrier gas He
Carrier gas flow rate, ml/min 19
Sample size, µl 1,0
Sample concentration, % (m/m) 2
Injector PTV or COC

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EN 15199-2:2006 (E)

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.

NOTE 1 The micro-syringe may be operated either manually or automatically.

NOTE 2 Plunger in needle syringes are not recommended due to excessive carry over of heavy ends to the following
analysis.

6.5 Volumetric flask, 10 ml capacity.

6.6 Refrigerator

NOTE It is recommended that the refrigerator be of an explosion-protected design.

6.7 Analytical balance, able to weigh with a precision of 0,1 mg.

7 Sampling procedure
Samples shall be taken as described in EN ISO 3170 or EN ISO 3171 and/or in accordance with the
requirements of national standards or regulations for the sampling of petroleum products. Store samples in
either glass or metal containers. Plastic containers for sample storage shall not be used as prolonged contact
with the sample can cause contamination of the sample due to possible leaching of the plasticizer.

8 Preparation of the apparatus

8.1 Gas chromatograph preparation

8.1.1 Set up and operate the gas chromatograph in accordance with the manufacturer’s instructions.

Typical operating conditions are shown in Table 2.

8.1.2 Deposits may form on the jet from combustion of decomposition products from the liquid stationary
phase. These will affect the characteristics of the detector and shall be removed.

NOTE The following parameters are affected by deposits on the jet: increase in inlet pressure; FID difficult to light;
increase in the CS2 response and an off specification reference material. 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 B.

9 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 (0.5) and add 5 ml to 7 ml carbon disulfide.

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 EN 15199-2:2006 (E)

CAUTION — It is recommended that all work with carbon disulfide is 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 applied:

%m ( V )= m 100m1
 m 
(1)
 1σ  +  2 σ 
 1  2

where

m1 is the mass of the test portion, in grams;

m2 is the mass of carbon disulfide, in grams;

σ1 is the density of the test portion at 20 °C, in kilograms per litre;

σ2 is the density of carbon disulfide at 20 °C, in kilograms per litre (= 1,26).

NOTE 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.

10 Calibration
10.1 Proceed in accordance with 10.2 to 10.4 each day before sample analysis. The first run of the day shall
not be a blank, a reference standard (5.9) or a test portion, but it may be the calibration mixture (5.8).

10.2 Run the calibration mixture (5.8) using the specified procedure described in Clause 11.

NOTE Take care to ensure the test portion volume chosen does not allow any peak to exceed the linear range of the
detector, or overload the column. A skew of > 3 indicates the sample is too concentrated and a skew of < 1 indicates an
old column or dirty liner. As a guide, 1 µl of the calibration mixture (5.8) has been found to be suitable for columns with film
thickness less than 0,17 µm.

10.3 Record the retention time of each component and plot the retention time versus the atmospheric boiling
point for each component to obtain the calibration curve.

NOTE The atmospheric boiling points of the alkanes are given in Annex C.

A typical chromatogram of the calibration mixture (5.8) is given in Figure 4 and a typical calibration curve is
given in Figure 5.

10.4 Run the reference material (5.9) using the specified procedure in Clause 11. Calculate the boiling range
distribution of the reference material by the procedures specified in Annex A and compare this with the
consensus values for the reference material used. If the results are not within the specified range, it is advised
to carefully follow the manufacturer's instructions regarding chromatographic problem solving and related
diagnostics.

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EN 15199-2:2006 (E)

Key:

A response
B retention time

Figure 4 — Typical chromatogram of calibration mixture

Key

A retention time
B temperature °C

Figure 5 — Typical calibration curve

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 EN 15199-2:2006 (E)

11 Procedure
11.1 Run a solvent (blank) baseline analysis before the first sample analysis, and then after every five
samples. Subtract blank baselines from subsequent analyses (see Figure 6).

NOTE It is good practice to follow each test portion with a carbon disulfide blank to prevent carryover of heavy non-
volatile material into the next analysis.

good baseline bad baseline bad baseline

merging parallel crossing
(high FBP) (low FBP)

Figure 6 — Baselines

The identification of a constant baseline at the end of the run is critical to the analysis. Constant attention shall
be given to all factors that influence baseline stability, e.g. column substrate bleed, septum bleed, detector
temperature control, constancy of carrier gas flow, leaks and instrument drift. The baseline at the end of each
analysis shall merge with the baseline of the blank run associated with it. Both signals shall merge to confirm
integrity; if they do not, the analysis shall be repeated.

11.2 Cool the column to the starting temperature, and inject the selected sample volume.

11.3 Immediately start programming the column temperature upward at a rate that produces the separation
specified in B.2.

11.4 Continue the run until the time for the highest component used for calibration has been exceeded.

12 Visual inspection of the chromatograms

Using the data system, expand the chromatogram of the secondary working standard or test portion, by
5 times. Merge the blank baseline and observe the following points:

The start of the area of interest is taken at a point on the baseline where the blank and the test portion
baselines are merged. This is taken before the start of the test portion and after the end of the solvent.

The end of the area of interest of the test portion is taken at the retention time equivalent to the required
temperature at which the recovery is determined.

The end of the area of interest of the secondary working standard is taken at a point on the baseline where
the blank and standard baselines are merged. This is taken before the end of the temperature programme.

The start of the test portion is determined as given in A.5.

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EN 15199-2:2006 (E)

The end of the test portion is determined as given in A.6.

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

14 Expression of results
Report the tabulated results as follows:

a) report all temperatures to the nearest 1 °C;

b) report all percentages to the nearest 1 % (m/m);

c) report the 0,5 % (m/m) point as the initial boiling point, and the recovery at selected final elution
temperature (720 ºC or 750 ºC);

d) report intermediate percentages as required, at intervals of not less than 1 % (m/m).

15 Precision

15.1 General

The precision was determined by statistical examination of inter-laboratory test results using EN ISO 4259 [4].

15.2 Repeatability

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 values given in Table 3 only in one case in twenty.

15.3 Reproducibility

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 values given in Table 3 only in one case in twenty.

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 EN 15199-2:2006 (E)

Table 3 — Precision values

% (m/m) recovered Repeatability (r) Reproducibility (R)
°C °C
IBP 2,1 8,7
5 0,9 3,8
10 0,7 3,3
20 0,8 3,6
30 0,8 4,1
40 1,2 5,2
50 1,4 6,7
60 2,0 6,7
70 2,9 6,4
80 4,0 6,7
90 5,9 9,5
95 8,1 13
Fractions Repeatability (r) Reproducibility (R)
%C % %
300 < 0,1 0,6
350 < 0,1 0,6
400 0,1 0,7
450 0,2 0,7
500 0,3 0,8
550 0,4 1,2
600 0,6 1,7
650 0,8 2,0
700 1,0 2,0
750 No data available No data available

16 Test report
The test report shall specify:

a) a reference to this European Standard, i.e. EN 15199-2;

b) the type and complete identification of the material tested;

c) the result of the test (see Clause 14);

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

e) date of the test.

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EN 15199-2:2006 (E)

Annex A
(normative)

Calculation procedure

A.1 Application
The algorithm given in this Annex only applies for a slice width of 0,1 s to 0,2 s (10 Hz to 5 Hz). The
chromatogram for the reference material (5.9), the sample, and the baseline shall be zeroed. The baseline
chromatogram is subtracted from the Reference Material 5010 (5.9.2) and from the sample chromatogram in
order to obtain the net area. An extended procedure is given as informative guidance in Annex D.

A.2 Starting conditions

The following data are required for the commencement of calculations:

i) sample data array (N data points);

ii) reference material data array (N data points);

iii) blank data array (N data points);

iv) processed data file from calibration run with retention times of normal alkanes;

v) boiling points of normal alkanes used in calibration run;

vi) start sample time;

vii) end sample time.

The data collection of the test portion or reference shall be identical to the used data points in the blank.

A.3 Zero sample or reference chromatogram

A.3.1 Subtract each blank slice area from the corresponding sample slice area.

A.3.2 Average the first twenty time slices from the subtracted slice areas.

A.3.3 Subtract the average slice area from each subtracted time slice to zero the chromatogram. Set negative
numbers to zero.

A.4 Sample area

Calculate the total sample area by summing each of the corrected area slices.

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 EN 15199-2:2006 (E)

A.5 Start of sample elution time

By inspection of the chromatogram, select a start time for the area of interest, after the elution of the solvent,
where the baseline merges with the blank. The time slice, after this point, where the average rate of change
first exceeds 0,000 01 %/s of the total area is defined as the start of sample. Report this time and/or indicate it
on the chromatogram.

A.6 End of sample elution time

The end of sample elution time is set by the user at 720 °C or 750 °C. It is the time equivalent to the
temperature at which the recovery is to be determined. This time shall be before the end of the temperature
programme.

A.7 End of reference material elution time

By inspection of the chromatogram, select the end time for the area of interest, before the end of the
temperature programme, where the baseline merges with the blank. The time slice, before this point, where
the average rate of change first exceeds 0,000 01 % / s of the total area is defined as the end of external
standard. Report this time and/or indicate it on the chromatogram.

A.8 Corrected sample or reference material area

Calculate the total corrected sample area by summing the area slices from the start of sample to the end of
sample.

A.9 Normalisation
A.9.1 Determine the area / weight factor for the reference material by summing all the area slices in the
external standard and dividing by the weight of the external standard taken in 10 ml carbon disulphide.

A.9.2 Determine the area / weight of the sample by summing all the area slices and dividing by the weight
of the sample taken in 10 ml carbon disulphide.

A.9.3 Determine the % recovery by:

 AS  A 
 W  ×  es W  × 100 (A.1)
 S   es 

where

As is the sum of the area slices of the sample determined in A.8;

Ws is the weight of sample taken in 10 ml carbon disulphide in 9.2;

Aes is the sum of the area slices of the reference material determined in A.8;

Wes is the weight of the reference material taken in 10 ml carbon disulphide in 9.2.

A.9.4 To convert time slices to area percents, start with the time slice corresponding to the start of the
sample and continue to the time slice corresponding to that set by the User and divide by the % recovery
determined in A.9.3.

17
EN 15199-2:2006 (E)

A.10 Conversion of retention time to percent off

A.10.1 Initial boiling point

Starting with the time slice corresponding to start of sample, add the normalised area percents until the total is
equal to, or greater than, 0,5 %. Linearly interpolate to find the time corresponding to exactly 0,5 % of the total
corrected sample area.

A.10.2 Intermediate boiling points

For each percent off between 1 % and 99 %, find the retention time where the cumulative area percent is
equal to or greater than the percent being determined. Use linear interpolation when the cumulative sum
exceeds the percent being determined.

A.11 Conversion of retention times to boiling points

A.11.1 For each retention time determined in A.10.1 to A.10.2, find the pair of calibration retention times that
bracket the percent off time of interest.

A.11.2 Calculate the boiling point corresponding to the percent off retention time, BPi, in °C, from the
following equation:

BPi = 
(BP2 − BP1 ) 
 (RT2 − RT1 ) ∗ (RTi − RT1 ) + BP1 (A.2)

where
RTi is the retention time for 1 percent off;
RT1 is the retention time of calibration point immediately below Ri;
RT2 is the retention time of calibration point immediately above Ri;
BP1 is the boiling point of compound at R1;
BP2 is the boiling point of compound at R2.

NOTE A report giving percent off at selected boiling point intervals can be calculated in an analogous manner.

Report all results in accordance with Clause 14.

18
 EN 15199-2:2006 (E)

Annex B
(normative)

System performance check

B.1 Frequency
Carry out a run on the calibration mixture (5.8), using identical conditions and injection volumes to those used
for the sample analysis, whenever:

a) the analytical system and conditions have been altered in any way since the last performance check
was carried out, or

b) the results obtained for the secondary working standard fall outside the permitted limits.

Determine the characteristics described in B.2 to B.4.

NOTE This procedure may be carried out as part of the boiling range calibration (see Clause 10).

B.2 Column resolution

Determine the column resolution, R, using the C50 and C52 peaks and the following equation:

2 (t 2 - t1)
R = (B.1)
1,699 (W 1 + W 2)

where

t1 is the retention time, in seconds, for the C50 peak;

t2 is the retention time, in seconds, for the C52 peak;

W1 is the width, in seconds, at half-height of C50 peak;

W2 is the width, in seconds, at half-height of C52 peak.

Resolution as determined above shall be at least 2, but no greater than 4.

B.3 Detector response (gravimetric blend)

Use a binary gravimetric blend (5.9.4) distillate to determine the detector response. Since the most critical
area of the chromatogram is where column bleeding occurs, the binary blend is also used as a recovery test.
The binary blend shall have the following characteristics:

a) the lower boiling distillate shall not interfere with the solvent;

b) there shall be a baseline between distillates;

c) the higher boiling point distillate shall elute totally and as close to the end of the temperature programme
as possible;

19
EN 15199-2:2006 (E)

d) the ratio of the areas of the two distillates shall be constant, which can be checked by measuring the %
recovered at 400 °C which shall be: (32,4 ± 0,6) % (m/m)..

If one of these criteria is not met, it is advised to carefully follow the manufacturer’s instructions regarding
chromatographic problem solving and related diagnostics.

B.4 Skewing of peak

Determine the skewing of the peak as the ratio A/B as shown in Figure B.1, for the C20 peak, where;

A is the width of the leading part of the peak at 5 % of the peak height;

B is the width of the following part of the peak at 5 % of the peak height.

The ratio shall not be less than 1 nor greater than 3.

Figure B.1 — Peak skewness

20
 EN 15199-2:2006 (E)

Annex C
(informative)

Boiling points of normal alkanes

The boiling points of normal alkanes used for construction of the calibration curve are given in Table C.1.

Table C.1 — Boiling points of normal alkanes

Carbon Boiling point Carbon Boiling point

number ºC number ºC
5 36 50 575
6 69 52 584
7 98 54 592
8 126 56 600
9 151 58 608
10 174 60 615
11 196 62 622
12 216 64 629
13 235 66 635
14 254 68 641
15 271 70 647
16 287 72 653
17 302 74 658
18 316 76 664
20 344 78 670
22 369 80 675
24 391 82 681
26 412 84 686
28 431 86 691
30 449 88 695
32 466 90 700
34 481 92 704
36 496 94 708
38 509 96 712
40 522 98 716
42 534 100 720
44 545 110 735
46 556 120 750
48 566 - -
NOTE Boiling points for carbon numbers above C60 are extrapolated.

21
EN 15199-2:2006 (E)

Annex D
(informative)

Additional guidance for the calculation algorithm

D.1 Zeroing of the reference material chromatogram

D.1.1 Examine the chromatogram obtained for Reference Material 5010 (5.9.2), and ensure, by visual
inspection of the chromatogram in the data system, that the first 5 slices contain neither sample nor solvent
elution.

D.1.2 Set up an array that contains slices obtained from the Reference Material 5010 chromatogram.
Calculate the average of the first five area slices. Subtract the average slice area from each slice in the
Reference Material 5010 chromatogram. Set negative numbers to zero.

D.1.3 Zero the blank baseline chromatogram by carrying out an analogous calculation as in D.1.2.

D.1.4 Subtract the blank baseline from the Reference Material 5010 chromatogram. Subtract each zeroed
blank baseline slice from the corresponding zeroed Reference Material 5010 slice. If there are negative slices,
set the slice values to zero.

D.1.5 Determine the end of elution time of Reference Material 5010.

NOTE Since it is a requirement that the sample chosen to obtain a response factor shall fully elute prior to the FEt
time, the end of sample elution for this chromatogram should be determined as described in EN 15199-1 [5], using the
algorithm to determine the time the signal of the completely eluted sample returns to baseline.

D.1.6 Determine the area of the chromatogram for Reference Material 5010. Determine the end time of
solvent elution. Sum all of the slices from the end of solvent elution to the end of sample elution. This is the
area of the standard, ASTD.

D.1.7 Calculate the boiling point distribution of Reference Material 5010. The resulting corrected slices
obtained for Reference Material 5010 are submitted to a calculation for boiling point distribution as in
EN 15199-1 [5]. A comparison of the values obtained with the consensus values listed in Table 1 is made and
all the boiling point values should fall within the specified windows. If this requirement is not met, correct any
chromatographic problems prior to proceeding with sample analysis.

Typical problems found in this step are: contaminated solvent; problems in sample preparation; sample
residue in the inlet or column, or both; quality of the baseline used, a partially blocked detector jet, or a
combination thereof.

D.2 Zeroing of sample chromatograms

D.2.1 In the case of crude oil analysis or samples in which the solvent peak is not resolved from the sample
components, ensure, by visual inspection of the chromatogram in the data system, that the first 5 slices
contain neither sample nor solvent elution. If there is sample elution, decrease the number of slices for the
averaging to 3.

D.2.2 Zero the sample chromatogram. Proceed in a manner analogous to that described in D.1.2.

D.2.3 Zero the blank baseline chromatogram. Carry out an analogous calculation as in D.1.3.

22
 EN 15199-2:2006 (E)

D.3 Blank baseline subtraction from the sample chromatogram

Carry out an analogous calculation as in D.1.4.

D.4 Quenching correction

D.4.1 For crude oil samples, a quenching factor is used to correct for the diminished FID response when the
CS2 co-elutes with sample components. This factor is applied to the time segment corresponding to the
elution of CS2. In the interlaboratory study, the factor of 1,930 was applied. This value is determined from
experiments made by dissolving butane, pentane, and hexane in toluene.

The solution is analyzed by injecting it under conditions identical to sample analysis. The areas for the
components are compared to the areas obtained by gradually adding weighed aliquots of CS2 to the original
solution. Samples that do not have components that co-elute with solvent, for example, residues or the
Reference Material 5010, do not require the quenching correction.

D.4.2 Determine the quenching interval. Select the time that the solvent peak starts to elute. Determine when
the solvent peak has eluted. Note the times of this interval in minutes.

D.4.3 Locate the slices of the quenching interval. For samples in which the solvent component co-elutes with
the sample chromatogram (that is, crude oils), determine the quenching interval, QI, as described in D.4.2.
Find the closest slice corresponding to the beginning of elution of the solvent peak as well as the final slice
corresponding to the end of elution of the solvent peak.

D.4.4 Correct the diminished response of the interval by multiplying each slice of this interval by the
quenching factor, QF. Use the value as discussed in D.4.1.

D.5 Determination of the sample final elution time (tFE)

Determine the time at which the oven reaches the isothermal portion of the temperature program. This is
usually recognized as an inflection point in the baseline. This point is called the final elution time (tFE). The
conversion of this slice to temperature will yield the final elution temperature, tFE. This conversion is carried out
in D.9.4.

D.6 Determination of the sample area

The net sample area is obtained by adding all slices from time t = 0 to the final elution time, tFE. This net area
is the ASMP.

D.7 Response factor

Calculate the response factor, RF, as follows:

( M STD ) 1
RF = × (D.1)
( M STD + M SLSTD ) ASTD

where

ASTD is the net area obtained for the Reference Material 5010 chromatogram after baseline subtraction and
after excluding the solvent peak (see D.1.6);

MSLSTD is the solvent mass, in grams, used for reference material dissolution;

23
EN 15199-2:2006 (E)

MSTD is the mass, in grams, of Reference Material 5010 used in preparing the response factor solution.

NOTE The mass term in Equation (D.1) is expressed as a fraction of the mass of solute and solvent.

D.8 Calculation of the percentage recovery

The percentage recovery, %RC, is defined as:

( ME ) ME × ( M SMP + M SLSMP )
% RC = × 100 = × 100 (D.2)
M SMP
( ( M SMP + M SLSMP )
) M SMP

where

ME is the mass, in grams, of the sample eluted;

MSMP is the sample mass, in grams;

MSLSMP is the mass of solvent, in grams, used in the sample solution.

Since:

ME = ( ASMP ) × ( RF ) (D.3)

where

ASMP is the net sample area;

RF is the response factor of the Reference Material 5010.

Substituting Equation (D.3) for the value of ME in Equation (D.2) yields:

ASMP × RF × ( M SMP + M SLSMP )

% RC = × 100 (D.4)
( M SMP )

Substituting (D.1) in (D.4) for the value of RF yields:

( M STD ) ( M SMP + M SLSMP ) ASMP

% RC = × × × 100 (D.5)
( M STD + M SLSTD ) M SMP ASTD

Determine whether the %recovery, (%RC) falls below the recovery threshold (Rt) limits set. If it is less than or
equal to the recovery threshold (Rt), use the %recovery (%RC) determined by Equation (D.5).
If the %recovery is greater than the recovery threshold (Rt), then the recovery is set to 100 %.
If the %recovery is larger than 102 % (1 standard deviation of the residue), repeat the analysis or determine
the chromatographic problem.

D.9 Determination of the boiling point distribution

D.9.1 Multiply each slice of the sample chromatogram by the %recovery as established in D.8. Divide each
slice by the total area of the sample obtained in D.6. This will express the slices in a percent scale.

24
 EN 15199-2:2006 (E)

D.9.2 Add the slices that will yield 0,5 %, 1 %, 2 %, . . . %recovery. Determine, at 1 % intervals, the time of
the slice yielding exactly 0,5 %, 1 %, 2 %, ...%recovery. Use an interpolation procedure to find the fractional
slices required to yield exactly 0,5 %, 1 %, ...2 %, ...%recovery.

D.9.3 Stop the calculation carried out in D.9.2 when obtaining a slice summation equal to the nearest whole
integer of the %recovery.

D.9.4 Convert the retention times to boiling points as outlined in the algorithm in A.11.2. Use the boiling point
temperatures listed in Table C.1. For each retention time obtained in D.9.2, find the corresponding
temperature from the boiling point vs. retention time function as shown in Figure 5. Calculate the
corresponding boiling points as determined in A.10.

D.10 Calculation of cut point intervals

D.10.1 For the two temperatures that define the cut point interval, find the two corresponding slices.

D.10.2 Using the calibration curve, convert this temperature range to a time range.

D.10.3 Convert the time range to a slice number range by multiplying by 60 and dividing by the slice width in
seconds.

D.10.4 Sum the normalized slices, starting with the initial slice of the cut and terminating with the last slice
after the cut. This sum will be equal to the %mass of the cut.

D.10.5 The %recovery, %RC, determined at a temperature TRC that is equal to or less than FET, can be
determined at a new temperature TN by using the following equation:

(% RCTRC − % RC −1% )
E RC = × (T − TRC −1% ) + % RC −1% (D.6)
(TRC − TRC −1% )

where

ERC is the estimated recovery at temperature T;

%RCTRC is the %recovery determined at temperature TRC in D.8;

%RC-1% is the %recovery determined at 1 % below the %RCTRC;

TRC-1% is the temperature corresponding to %RC-1%.

The use of this equation for values TN > TFE is not recommended.

25
EN 15199-2:2006 (E)

Bibliography

[1] IP 507/05, Petroleum products — Determination of boiling range distribution by gas chromatography
method — Part 2: Heavy distillates and residual fuel

[2] ASTM D7169-05, Standard test Method for Boiling Point Distribution of Samples with residues Such as
Crude Oils and Atmospheric and Vacuum Residues by High Temperature Gas Chromatography

[3] ISO 3924, Petroleum products — Determination of boiling range distribution — Gas chromatography
method.

[4] EN ISO 4259:1995, Petroleum products — Determination and application of precision data in relation
to methods of test (ISO 4259:1992, including Cor. 1:1993).

[5] EN 15199-1, Petroleum products — Determination of boiling range distribution by gas chromatography
method — Part 1: Middle distillates and lubricating base oils

26
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