Petroleum products - Determination of boiling range distribution - Gas chromatography method (ISO 3924:2016)

This International Standard specifies a method for the determination of the boiling range distribution of
petroleum products. The method is applicable to petroleum products and fractions with a final boiling
point of 538 °C or lower at atmospheric pressure as determined by this International Standard. This
International Standard is not applicable to gasoline samples or gasoline components. The method is
limited to products having a boiling range greater than 55 °C and having a vapour pressure sufficiently
low to permit sampling at ambient temperature.
The method has successfully been applied to samples containing fatty acid methyl esters (FAME) up to
10 % (V/V).
NOTE For the purposes of this International Standard, the terms “% (m/m)” and % (V/V) are used to
represent the mass fraction (μ), respectively the volume fraction (φ) of a material.

Mineralölerzeugnisse - Bestimmung der Siedebereichsverteilung - Gaschromatographisches Verfahren (ISO 3924:2016)

Produits pétroliers - Détermination de la répartition dans l'intervalle de distillation - Méthode par chromatographie en phase gazeuse (ISO 3924:2016)

ISO 3924:2016 spécifie une méthode pour déterminer la répartition dans l'intervalle de distillation des produits pétroliers. La méthode est applicable aux produits pétroliers et aux fractions pétrolières dont le point final de distillation est inférieur ou égal à 538 °C à la pression atmosphérique quand il est mesuré en appliquant la présente Norme internationale. La présente Norme internationale n'est pas adaptée au cas des essences ou composés à base d'essences. Le domaine d'application de la méthode est limité aux produits dont l'intervalle de distillation est supérieur à 55 °C et dont la pression de vapeur est suffisamment basse pour permettre un échantillonnage à la température ambiante.
La méthode a été appliquée avec succès à des échantillons contenant des esters méthyliques d'acides gras (EMAG) jusqu'à 10 % (V/V).

Naftni proizvodi - Določevanje destilacijskega območja - Metoda plinske kromatografije (ISO 3924:2016)

Ta mednarodni standard določa metodo za določevanje destilacijskega območja naftnih proizvodov. Metoda se uporablja za naftne proizvode in frakcije z zgornjo točko vretja pri temperaturi 538 °C ali manj pri atmosferskem tlaku, kot je določeno v tem mednarodnem standardu. Ta mednarodni standard se ne uporablja za vzorce bencina ali sestavine bencina. Metoda je omejena na proizvode z destilacijskim območjem nad 55 °C in dovolj nizkim parnim tlakom, ki zagotavlja vzorčenje pri temperaturi okolja.
Metoda se uspešno uporablja za vzorce, ki vsebujejo do 10 % (V/V) metil estrov maščobnih kislin (FAME).
OPOMBA: Za namene tega evropskega standarda sta uporabljeni oznaki »% (m/m)« in »% (V/V)«, ki predstavljata masni delež (μ) oziroma prostornino (φ) materiala.

General Information

Status
Withdrawn
Public Enquiry End Date
04-Oct-2015
Publication Date
07-Nov-2016
Withdrawal Date
17-Sep-2019
Current Stage
9900 - Withdrawal (Adopted Project)
Start Date
18-Sep-2019
Due Date
11-Oct-2019
Completion Date
18-Sep-2019

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SLOVENSKI STANDARD
SIST EN ISO 3924:2016
01-december-2016
1DGRPHãþD
SIST EN ISO 3924:2010
1DIWQLSURL]YRGL'RORþHYDQMHGHVWLODFLMVNHJDREPRþMD0HWRGDSOLQVNH
NURPDWRJUDILMH ,62
Petroleum products - Determination of boiling range distribution - Gas chromatography
method (ISO 3924:2016)
Mineralölerzeugnisse - Bestimmung der Siedebereichsverteilung -
Gaschromatographisches Verfahren (ISO 3924:2016)
Produits pétroliers - Détermination de la répartition dans l'intervalle de distillation -
Méthode par chromatographie en phase gazeuse (ISO 3924:2016)
Ta slovenski standard je istoveten z: EN ISO 3924:2016
ICS:
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
75.080 Naftni proizvodi na splošno Petroleum products in
general
SIST EN ISO 3924:2016 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST EN ISO 3924:2016

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SIST EN ISO 3924:2016


EN ISO 3924
EUROPEAN STANDARD

NORME EUROPÉENNE

October 2016
EUROPÄISCHE NORM
ICS 75.080 Supersedes EN ISO 3924:2010
English Version

Petroleum products - Determination of boiling range
distribution - Gas chromatography method (ISO
3924:2016)
Produits pétroliers - Détermination de la répartition Mineralölerzeugnisse - Bestimmung des Siedeverlaufs -
dans l'intervalle de distillation - Méthode par Gaschromatographisches Verfahren (ISO 3924:2016)
chromatographie en phase gazeuse (ISO 3924:2016)
This European Standard was approved by CEN on 15 July 2016.

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, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, 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: Avenue Marnix 17, B-1000 Brussels
© 2016 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 3924:2016 E
worldwide for CEN national Members.

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SIST EN ISO 3924:2016
EN ISO 3924:2016 (E)
Contents Page
European foreword . 3

2

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SIST EN ISO 3924:2016
EN ISO 3924:2016 (E)
European foreword
This document (EN ISO 3924:2016) has been prepared by Technical Committee ISO/TC 28 “Petroleum
products and related products of synthetic or biological origin” in collaboration with 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 2017, and conflicting national standards shall be
withdrawn at the latest by April 2017.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent
rights.
This document supersedes EN ISO 3924:2010.
According to the CEN-CENELEC Internal Regulations, the national standards organizations of the
following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria,
Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia,
France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta,
Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey and the United Kingdom.
Endorsement notice
The text of ISO 3924:2016 has been approved by CEN as EN ISO 3924:2016 without any modification.
3

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SIST EN ISO 3924:2016

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SIST EN ISO 3924:2016
INTERNATIONAL ISO
STANDARD 3924
Fourth edition
2016-09-15
Petroleum products — Determination
of boiling range distribution — Gas
chromatography method
Produits pétroliers — Détermination de la répartition dans l’intervalle
de distillation — Méthode par chromatographie en phase gazeuse
Reference number
ISO 3924:2016(E)
©
ISO 2016

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SIST EN ISO 3924:2016
ISO 3924:2016(E)

COPYRIGHT PROTECTED DOCUMENT
© ISO 2016, Published in Switzerland
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form
or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior
written permission. Permission can be requested from either ISO at the address below or ISO’s member body in the country of
the requester.
ISO copyright office
Ch. de Blandonnet 8 • CP 401
CH-1214 Vernier, Geneva, Switzerland
Tel. +41 22 749 01 11
Fax +41 22 749 09 47
copyright@iso.org
www.iso.org
ii © ISO 2016 – All rights reserved

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SIST EN ISO 3924:2016
ISO 3924:2016(E)

Contents Page
Foreword .iv
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 1
4 Principle . 2
5 Reagents and materials . 2
6 Apparatus . 4
7 Sampling . 6
8 Preparation of apparatus . 6
9 Calibration . 9
9.1 Analysis sequence protocol . 9
9.2 Baseline compensation analysis .10
9.3 Retention time versus boiling point calibration .10
9.4 Analysis of reference material .10
10 Procedure.12
10.1 Sample preparation .12
10.2 Sample analysis .12
11 Calculation .13
12 Expression of results .13
13 Precision .14
13.1 General .14
13.2 Repeatability .14
13.3 Reproducibility .14
14 Test report .15
Annex A (informative) Calculation of ISO 3405 equivalent data .16
Annex B (informative) Accelerated analysis .19
Annex C (informative) Boiling points of non-normal alkane hydrocarbons .21
Bibliography .25
© ISO 2016 – All rights reserved iii

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SIST EN ISO 3924:2016
ISO 3924:2016(E)

Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards
bodies (ISO member bodies). The work of preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical
committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of
electrotechnical standardization.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of
any patent rights identified during the development of the document will be in the Introduction and/or
on the ISO list of patent declarations received (see www.iso.org/patents).
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation on the meaning of ISO specific terms and expressions related to conformity
assessment, as well as information about ISO’s adherence to the WTO principles in the Technical
Barriers to Trade (TBT) see the following URL: Foreword - Supplementary information
ISO 3924 was prepared by the European Committee for Standardization (CEN) Technical Committee
CEN/TC 19, Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological
origin, in collaboration with ISO Technical Committee ISO/TC 28, Petroleum products and related
products of synthetic or biological origin, in accordance with the Agreement on technical cooperation
between ISO and CEN (Vienna Agreement).
This fourth edition cancels and replaces the third edition (ISO 3924:2010), which has been technically
[1]
revised. The third edition had several updates regarding the calculation of ISO 3405 equivalent data.
Because ISO 3924 is extensively used and referenced in many fuel specifications, a faster analysis
procedure was included. Many fuel specifications concerned demand volume percentage recovered
at 250°C and 350°C but this result was not part of the report of ISO 3924 in the former version as
described. This is updated with this edition (see Annex A), for which an assessment has been executed
by CEN/TC 19. In addition, several editorial updates have been made.
[3] [4]
This method is originally based on the jointed IP 406 and ASTM D2887 methods.
iv © ISO 2016 – All rights reserved

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SIST EN ISO 3924:2016
INTERNATIONAL STANDARD ISO 3924:2016(E)
Petroleum products — Determination of boiling range
distribution — Gas chromatography method
WARNING — — The use of this International Standard can involve hazardous materials,
operations and equipment. This International Standard does not purport to address all of the
safety problems associated with its use. It is the responsibility of users of this International
Standard to take appropriate measures to ensure the safety and health of personnel prior to
application of the standard, and fulfil statutory and regulatory requirements for this purpose.
1 Scope
This International Standard specifies a method for the determination of the boiling range distribution of
petroleum products. The method is applicable to petroleum products and fractions with a final boiling
point of 538 °C or lower at atmospheric pressure as determined by this International Standard. This
International Standard is not applicable to gasoline samples or gasoline components. The method is
limited to products having a boiling range greater than 55 °C and having a vapour pressure sufficiently
low to permit sampling at ambient temperature.
The method has successfully been applied to samples containing fatty acid methyl esters (FAME) up to
10 % (V/V).
NOTE For the purposes of this International Standard, the terms “% (m/m)” and % (V/V) are used to
represent the mass fraction (µ), respectively the volume fraction (φ) of a material.
2 Normative references
The following documents, in whole or in part, are normatively referenced in this document and are
indispensable for its application. For dated references, only the edition cited applies. For undated
references, the latest edition of the referenced document (including any amendments) applies.
ISO 3170, Petroleum liquids — Manual sampling
ISO 3171, Petroleum liquids — Automatic pipeline sampling
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
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
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SIST EN ISO 3924:2016
ISO 3924:2016(E)

3.3
slice rate
number of data slices acquired per unit of time used to integrate the continuous (analogue)
chromatographic detector response during an analysis
Note 1 to entry: The slice rate is expressed in Hz (for example, slices per second).
4 Principle
A sample is introduced into a gas chromatographic column which separates hydrocarbons in the order
of increasing boiling point. The column temperature is raised at a reproducible rate and the area under
the chromatogram is recorded throughout the analysis. Boiling temperatures are assigned to the time
axis from a calibration curve, obtained under the same conditions by running a known mixture of
hydrocarbons covering the boiling range expected in the sample. From these data, the boiling range
distribution is obtained.
Annex A presents a correlation model for the calculation of physical distillation (see References [1], [5]
and [6]) equivalent data from boiling range distribution analysis by gas chromatography determined
following this International Standard.
Annex B describes an alternative, accelerated analysis (see 8.2).
5 Reagents and materials
5.1 Stationary phase for columns, non-polar, that elutes hydrocarbons in boiling point order.
NOTE The following materials have been used successfully as liquid phases.
For packed columns:
— silicone gum rubber UC-W98;
— silicone gum rubber GE-SE-30;
— silicone gum rubber OV-1;
— silicone gum rubber OV-101;
For capillary columns:
— polydimethylsiloxane.
5.2 Solid support for packed columns, usually consisting of crushed fire brick or chromatographic
diatomaceous earth.
The particle size and support loading shall be such as to give optimum resolution and analysis time.
NOTE In general, support loadings of 3 % to 10 % have been found most satisfactory.
5.3 Carrier gas, with a minimum purity of 99,995 %, constituted of
a) helium or hydrogen for use with thermal conductivity detectors, or
b) nitrogen, helium, hydrogen or argon for use with flame ionization detectors.
5.4 Hydrogen, grade suitable for flame ionization detectors.
5.5 Compressed air, free of oil and water, regulated for flame ionization detectors.
2 © ISO 2016 – All rights reserved

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SIST EN ISO 3924:2016
ISO 3924:2016(E)

5.6 Calibration mixture, consisting of an accurately weighed mixture of n-alkanes covering the range
from C to C and dissolved in carbon disulfide (5.8).
5 44
For packed columns, the final concentration should be approximately 10 parts of the alkane mixture to
100 parts of carbon disulfide. For capillary columns, the final concentration should be approximately 1
part of the alkane mixture to 100 parts of carbon disulfide.
The following mixture of alkanes has been found to be satisfactory for most samples: C , C , C , C , C ,
5 6 7 8 9
C , C , C , C , C , C , C , C , C , C , C , C . At least one component of the mixture shall have a
10 12 14 16 18 20 24 28 32 36 40 44
boiling point lower than the initial boiling point of the sample and at least one component shall have a
boiling point higher than the final boiling point of the sample. The boiling points of alkanes are listed in
Table 1.
Table 1 — Boiling points of normal alkanes
Carbon no. Boiling point Carbon no. Boiling point
°C °C
2 −89 24 391
3 −42 25 402
4 0 26 412
5 36 27 422
6 69 28 431
7 98 29 440
8 126 30 449
9 151 31 458
10 174 32 466
11 196 33 474
12 216 34 481
13 235 35 489
14 254 36 496
15 271 37 503
16 287 38 509
17 302 39 516
18 316 40 522
19 330 41 528
20 344 42 534
21 356 43 540
22 369 44 545
23 380
[7]
NOTE API Project 44, October 31, 1972 , is believed to have provided the original normal paraffin boiling point data
that were listed in former editions of this International Standard. However, over the years some of the data contained in
both API Project 44 (Thermodynamics Research Center Hydrocarbon Project) and the test methods have changed, and they
are no longer equivalent. This Table represents the current normal paraffin boiling point values accepted by ISO, ASTM and
the Energy Institute.
If the test sample contains significant quantities of n-alkanes which can be identified on the
chromatogram, these peaks may be used as internal boiling point calibration points. However, it is
advisable to use the calibration mixture to be sure of peak identifications.
Propane and butane may be added non-quantitatively to the calibration mixture, if necessary, to comply
with 5.6. This may be done by bubbling a small amount of the gaseous hydrocarbon into a septum-
sealed vial of the calibration mixture using a gas syringe.
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SIST EN ISO 3924:2016
ISO 3924:2016(E)

If stationary phases other than those listed in the note in 5.1 are used, the retention times of a few
alkylbenzenes across the boiling range such as o-xylene, n-butylbenzene, 1,3,5-tri-isopropylbenzene,
n-decylbenzene and n-tetradecylbenzene shall also be checked to make certain that the column is
separating according to the boiling point order (see Annex C).
5.7 Reference material, the primary reference material used shall be the ASTM Reference Gas Oil No.1.
5.8 Carbon disulfide, reagent grade (CAS RN 75-15-0).
6 Apparatus
6.1 Chromatograph, any gas chromatograph that has the following performance characteristics may
be used.
6.1.1 Detector, of either the flame ionization or thermal conductivity type.
The detector shall have sufficient sensitivity to detect a mass fraction of 1,0 % of dodecane with a peak
height of at least 10 % of full scale on the recorder under the conditions specified in this International
Standard, and without loss of resolution as defined in 8.3. When operating at this sensitivity level,
detector stability shall be such that a baseline drift of not more than 1 % of full scale per hour is
obtained. The detector shall be capable of operating continuously at a temperature equivalent to the
maximum column temperature employed. The detector shall be connected to the column in such a way
that any cold spots between the detector and the column are avoided.
NOTE It is not desirable to operate thermal conductivity detectors at a temperature higher than the
maximum column temperature employed. Operation at higher temperatures only serves to shorten the useful
life of the detector, and generally contributes to higher noise levels and greater drift.
6.1.2 Column temperature programmer, capable of programmed temperature operation over a
range sufficient to establish a retention time of at least 1 min for the initial boiling point and to elute the
entire sample within the temperature ramp.
The programming rate shall be sufficiently reproducible to obtain retention time repeatability of 6 s for
each component in the calibration mixture (5.6).
If the initial boiling point is less than approximately 93 °C, an initial column temperature below ambient
can be required. However, excessively low initial column temperatures shall be avoided, to ensure that
the stationary phase remains liquid. The initial temperature of the column shall be only low enough to
obtain a calibration curve meeting the requirements of this International Standard.
6.1.3 Sample inlet system, either be capable of operating continuously at a temperature equivalent
to the maximum column temperature employed or provide on-column injection with some means
of programming the entire column, including the point of sample introduction, up to the maximum
temperature required.
The sample inlet system shall be connected to the chromatographic column in such a way that any cold
spots between the inlet system and the column are avoided.
6.2 Column, any column and conditions may be used, provided that, under the conditions of the test,
separations are in the order of boiling points as given in Table 1, and the column resolution, CR, is at least
3 (8.3). Typical column operating conditions are given in Table 2 and 3.
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SIST EN ISO 3924:2016
ISO 3924:2016(E)

Table 2 — Typical operating conditions for packed columns
Packed columns 1 2
Column length, (m) 0,7 0,5
Column outside diameter, (mm) 3,2 3,2
Stationary phase OV-101 UC-W98
Percent stationary phase 5 10
a b
Support material G P
Support mesh size (μm) 80/100 80/100
Initial column temperature, (°C) −40 −30
Final column temperature, (°C) 350 360
Programming rate, (°C/min) 10 10
Carrier gas Helium Nitrogen
Carrier gas flow, (ml/min) 30 25
Detector FID FID
Detector temperature, (°C) 370 360
Injection-port temperature, (°C) 370 350
Sample size, (μl) 0,5 1
a
Chromosorb® G (AW-DMS).
b
Chromosorb® P (AW).
Table 3 — Typical operating conditions for capillary columns
Capillary columns 3 4 5
Column length (m) 7,5 5 10
Column inner diameter (mm) 0,53 0,53 0,53
Column DB-1 HP-1 HP-1
Stationary phase thickness (μm) 1,5 0,88 2,65
Carrier gas Nitrogen Helium Helium
Carrier gas flow rate (ml/min) 30 12 20
Initial column temperature (°C) 40 35 40
Final column temperature (°C) 340 350 350
Programming rate (°C/min) 10 10 15
Detector FID FID FID
Detector temperature (°C) 350 380 350
Injector temperature (°C) 340 Cool on-column type Programmed
temperature
vaporization type
Sample size (μl) 0,5 1 0,2
Sample concentration [% (m/m)] 25 10 Neat
6.3 Recorder/plotter, this apparatus is used for plotting the chromatogram. This may be accomplished
using a 0 mV to 1 mV recording potentiometer having a full-scale response time of 2 s or less and a
minimum chart width of approximately 120 mm. Alternatively, a computer or other device may be used,
provided it is capable of graphics presentation of the same or better quality as a potentiometric recorder.
6.4 Integrator/computer, this apparatus is used for determining the accumulated area under the
chromatogram. This may be achieved by using a computer-based chromatography data system or an
electronic integrator. The integrator/computer system shall have normal chromatographic software for
measuring the retention times and areas of eluting peaks. In addition, the system shall be capable of
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SIST EN ISO 3924:2016
ISO 3924:2016(E)

converting the continuously integrated detector signal into area slices of fixed duration. These contiguous
area slices, collected for the entire analysis, shall be stored for later processing. The electronic range of
the integrator/computer (e.g. 1 V) shall be within the linear range of the detector/electrometer system
used. The system shall be capable of subtracting the area slice of a blank run from the corresponding
area slice of a sample run.
NOTE Some gas chromatographs have an algorithm built into their operating software that allows a
mathematical model of the baseline profile to be stored in the memory. This profile can be automatically
subtracted from the detector signal on subsequent sample analysis to compensate for any baseline offset. Some
integration systems also store and automatically subtract a blank analysis from subsequent sample analysis.
6.5 Flow/pressure controllers.
6.5.1 If a packed column is used, the chromatograph shall be equipped with constant-flow controllers
capable of maintaining the carrier gas flow constant to ±1 % over the full operating temperature range.
6.5.2 If a wide-bore capillary column is used, the chromatograph shall be equipped with a controller
of carrier gas flow or pressure appropriate for the inlet used.
6.6 Micro-syringe, this apparatus is used to introduce the sample into the chromatograph. Sample
injection may be either manual or automatic. Automatic sample injection is preferred because it gives
better retention time precision.
7 Sampling
Unless otherwise specified, samples shall be taken by the procedures described in ISO 3170 or ISO 3171.
8 Preparation of apparatus
8.1 Column preparation, any satisfactory metho
...

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