ASTM D6352-04(2009)

This document is not anASTM standard and is intended only to provide the user of anASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
An American National Standard
Designation:D6352–03 Designation: D 6352 – 04 (Reapproved 2009)
Standard Test Method for
Boiling Range Distribution of Petroleum Distillates in
Boiling Range from 174 to 700°C by Gas Chromatography
This standard is issued under the fixed designation D 6352; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope *
1.1 This test method covers the determination of the boiling range distribution of petroleum distillate fractions.The test method
is applicable to petroleum distillate fractions having an initial boiling point greater than 174°C (345°F) and a final boiling point
of less than 700°C (1292°F) (C10 to C90) at atmospheric pressure as measured by this test method.
1.2 The test method is not applicable for the analysis of petroleum or petroleum products containing low molecular weight
components (for example naphthas, reformates, gasolines, crude oils). Materials containing heterogeneous components (for
example alcohols, ethers, acids, or esters) or residue are not to be analyzed by this test method. SeeTest Methods D 3710, D 2887,
or D 5307 for possible applicability to analysis of these types of materials.
1.3 The values stated in SI units are to be regarded as standard. The values stated in inch-pound units are for information only
and may be included as parenthetical values.
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory
limitations prior to use.
2. Referenced Documents
2.1 ASTM Standards:
D86 Test Method for Distillation of Petroleum Products at Atmospheric Pressure
D 1160 Test Method for Distillation of Petroleum Products at Reduced Pressure
D 2887 Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography
D 2892 Test Method for Distillation of Crude Petroleum (15-Theoretical Plate Column)
D 3710 Test Method for Boiling Range Distribution of Gasoline and Gasoline Fractions by Gas Chromatography
D 4626 Practice for Calculation of Gas Chromatographic Response Factors
D 5307 Test Method for Determination of Boiling Range Distributions of Crude Petroleum by Gas Chromatography
E 355 Practice for Gas Chromatography Terms and Relationships
E 594 Practice for Testing Flame Ionization Detectors Used in Gas or Supercritical Fluid Chromatography
E 1510 Practice for Installing Fused Silica Open Tubular Capillary Columns in Gas Chromatographs
3. Terminology
3.1 Definitions—Thistestmethodmakesreferencetomanycommongaschromatographicprocedures,terms,andrelationships.
For definitions of these terms used in this test method, refer to Practices E 355, E 594, and E 1510.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 area slice—the area resulting from the integration of the chromatographic detector signal within a specified retention time
interval. In area slice mode (see 6.4.2), peak detection parameters are bypassed and the detector signal integral is recorded as area
slices of consecutive, fixed duration time intervals.
3.2.2 corrected area slice—an area slice corrected for baseline offset by subtraction of the exactly corresponding area slice in
a previously recorded blank (non-sample) analysis.
3.2.3 cumulative corrected area—the accumulated sum of corrected area slices from the beginning of the analysis through a
given retention time, ignoring any non-sample area (for example, solvent).
This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products and Lubricants and is the direct responsibility of Subcommittee D02.04 on
Hydrocarbon Analysis.
Current edition approved Nov. 1, 2003. Published November 2003. Originally approved in 1998. Last previous edition approved in 2002 as D6352–02.on Petroleum
Products and Lubricants and is the direct responsibility of Subcommittee D02.04.0H on Chromatographic Distribution Methods.
´1
Current edition approved April 15, 2009. Published July 2009. Originally approved in 1998. Last previous edition approved in 2004 as D 6352 – 04 .
For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
*A Summary of Changes section appears at the end of this standard.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D 6352 – 04 (2009)
3.2.4 final boiling point (FBP)—the temperature (corresponding to the retention time) at which a cumulative corrected area
count equal to 99.5 % of the total sample area under the chromatogram is obtained.
3.2.5 initial boiling point (IBP)—the temperature (corresponding to the retention time) at which a cumulative corrected area
count equal to 0.5 % of the total sample area under the chromatogram is obtained.
3.2.6 slice rate—the time interval used to integrate the continuous (analog) chromatographic detector response during an
analysis. The slice rate is expressed in Hz (for example integrations or slices per second).
3.2.7 slice time—the analysis time associated with each area slice throughout the chromatographic analysis. The slice time is
the time at the end of each contiguous area slice.
3.2.8 total sample area—the 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.
3.3 Abbreviations— A common abbreviation of hydrocarbon compounds is to designate the number of carbon atoms in the
compound.Aprefix is used to indicate the carbon chain form, while a subscripted suffix denotes the number of carbon atoms (for
example n-C for normal-decane, i-C for iso-tetradecane).
10 14
4. Summary of Test Method
4.1 Theboilingrangedistributiondeterminationbydistillationissimulatedbytheuseofgaschromatography.Anon-polaropen
tubular (capillary) gas chromatographic column is used to elute the hydrocarbon components of the sample in order of increasing
boiling point.
4.2 A sample aliquot is diluted with a viscosity reducing solvent and introduced into the chromatographic system. Sample
vaporization is provided by separate heating of the point of injection or in conjunction with column oven heating.
4.3 The column oven temperature is raised at a specified linear rate to effectaffect separation of the hydrocarbon components
in order of increasing boiling point. The elution of sample components is quantitatively determined using a flame ionization
detector. The detector signal is recorded as area slices for consecutive retention time intervals during the analysis.
4.4 Retention times of known normal paraffin hydrocarbons, spanning the scope of the test method, are determined and
correlated to their boiling point temperatures. The normalized cumulative corrected sample areas for each consecutive recorded
time interval are used to calculate the boiling range distribution. The boiling point temperature at each reported percent off
increment is calculated from the retention time calibration.
5. Significance and Use
5.1 The boiling range distribution of medium and heavy petroleum distillate fractions provides an insight into the composition
of feed stocks and products related to petroleum refining processes (for example, hydrocracking, hydrotreating, visbreaking, or
deasphalting). The gas chromatographic simulation of this determination can be used to replace conventional distillation methods
for control of refining operations. This test method can be used for product specification testing with the mutual agreement of
interested parties.
5.2 This test method extends the scope of boiling range determination by gas chromatography to include medium and heavy
petroleum distillate fractions beyond the scope of Test Method D 2887 (538°C).
5.3 Boiling range distributions obtained by this test method have not been analyzed for correlation to those obtained by low
efficiency distillation, such as with Test Method D 86 or D 1160.
6. Apparatus
6.1 Chromatograph— The gas chromatographic system used shall have the following performance characteristics:
6.1.1 Carrier Gas Flow Control—The chromatograph shall be equipped with carrier gas pressure or flow control capable of
maintaining constant carrier gas flow control through the column throughout the column temperature program cycle.
6.1.2 Column Oven— Capable of sustained and linear programmed temperature operation from near ambient (for example, 30
to 35°C) up to 450°C.
6.1.3 Column Temperature Programmer —The chromatograph shall be capable of linear programmed temperature operation up
to 450°C at selectable linear rates up to 20°C/min. The programming rate shall be sufficiently reproducible to obtain the retention
time repeatability of 0.1 min (6 s) for each component in the calibration mixture described in 7.5.
6.1.4 Detector—This test method requires the use of a flame ionization detector (FID). The detector shall meet or exceed the
followingspecificationsasdetailedininaccordancewithPracticeE 594.Theflamejetshouldhaveanorificeofapproximately0.05
to 0.070 mm (0.020 to 0.030 in.).
6.1.4.1 Operating Temperature—100 to 450°C.
6.1.4.2 Sensitivity— >0.005 C/g carbon.
6.1.4.3 Minimum Detectability—1 3 10-11 g carbon/s.
6.1.4.4 Linear Range— >10
6.1.4.5 Connectionofthecolumntothedetectorshallbesuchthatnotemperaturebelowthecolumntemperatureexistsbetween
the column and the detector. Refer to Practice E 1510 for proper installation and conditioning of the capillary column.
6.1.5 Sample Inlet System—Any sample inlet system capable of meeting the performance specification in 7.6 and 8.2.2 may be
used. Programmable temperature vaporization (PTV) and cool on-column injection systems have been used successfully.
D 6352 – 04 (2009)
6.2 Microsyringe—Amicrosyringe with a 23-gage or smaller stainless steel needle is used for on-column sample introduction.
Syringes of 0.1 to 10-µL capacity are available.
6.2.1 Automatic syringe injection is recommended to achieve best precision.
6.3 Column—This test method is limited to the use of non-polar wall coated open tubular (WCOT) columns of high thermal
stability (see Note 1). Glass, fused silica, and stainless steel columns with 0.53 to 0.75-mm internal diameter have been
successfully used. Cross-linked or bonded 100 % dimethyl-polysiloxane stationary phases with film thickness of 0.10 to 0.20 µm
have been used.The column length and liquid phase film thickness shall allow the elution of at least C90 n-paraffin (BP= 700°C).
The column and conditions shall provide separation of typical petroleum hydrocarbons in order of increasing boiling point and
meet the column performance requirements of 8.2.1. The column shall provide a resolution between three (3) and ten (10) using
the test method operating conditions.
NOTE 1—Based on recent information that suggests that true boiling points (atmospheric equivalent temperatures) versus retention times for all
components do not fall on the same line, other column systems that can meet this criteria will be considered.These criteria will be specified after a round
robin evaluation of the test method is completed.
6.4 Data Acquisition System:
6.4.1 Recorder—A 0 to 1 mV range recording potentiometer or equivalent with a full-scale response time of2sor less may
be used. It is, however, not a necessity if an integrator/computer data system is used.
6.4.2 Integrator—Means shall be provided for determining the accumulated area under the chromatogram.This can be done by
means of an electronic integrator or computer-based chromatography data system. The integrator/computer system shall have
normal chromatographic software for measuring the retention time and areas of eluting peaks (peak detection mode). In addition,
the system shall be capable of converting the continuously integrated detector signal into area slices of fixed duration. These
contiguous area slices, collected for the entire analysis, are stored for later processing. The electronic range of the
integrator/computer (for example 1 V, 10 V) shall be operated within the linear range of the detector/electrometer system used.
NOTE 2—Some gas chromatographs have an algorithm built into their operating software that allows a mathematical model of the baseline profile to
be stored in memory. This profile is automatically subtracted from the detector signal on subsequent sample runs to compensate for the column bleed.
Some integration systems also store and automatically subtract a blank analysis from subsequent analytical determinations.
7. Reagents and Materials
7.1 Carrier Gas— Helium, hydrogen, or nitrogen of high purity (Warning—Helium and nitrogen are compressed gases under
high pressure). Additional purification is recommended by the use of molecular sieves or other suitable agents to remove water,
oxygen, and hydrocarbons. Available pressure shall be sufficient to ensure a constant carrier gas flow rate.
7.2 Hydrogen—Hydrogen of high purity (for example, hydrocarbon free) is used as fuel for the FID. Hydrogen can also be
suedused as the carrier gas. (Warning—Hydrogen is an extremely flammable gas under high pressure).
7.3 Air—High purity (for example, hydrocarbon free) compressed air is used as the oxidant for the FID. (Warning—
Compressed air is a gas under high pressure and supports combustion).
7.4 Solvents—Unless otherwise indicated, it is intended that all solvents conform to the specifications of the Committee on
Analytical Reagents of the American Chemical Society where such specifications are available. Other grades may be used,
provided it is first ascertained that the solvent is of sufficiently high purity to permit its use without lessening the accuracy of the
determination.
7.4.1 Carbon Disulfide (CS )—(99+ % pure) is used as a viscosity-reducing solvent and as a means of reducing mass of sample
introduced onto the column to ensure linear detector response and reduced peak skewness. It is miscible with asphaltic
hydrocarbons and provides a relatively small response with the FID. The qualit
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