ASTM D7213-23

Standard Test Method for Boiling Range Distribution of Petroleum Distillates in the Boiling Range from 100 °C to 615 °C by Gas Chromatography

SIGNIFICANCE AND USE
5.1 The boiling range distribution of light and medium petroleum distillate fractions provides an insight into the composition of feed stocks and products related to petroleum refining process, This gas chromatographic determination of boiling range 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 light and medium petroleum distillate fractions beyond the scope of Test Method D2887 (538 °C) and below Test Method D6352 (700 °C).  
5.3 Boiling range distributions obtained by this test method are theoretically equivalent to those obtained by true boiling point (TBP) distillation (see Test Method D2892). They are not equivalent to results from low efficiency distillation such as those obtained with Test Method D86 or D1160.
SCOPE
1.1 This test method covers the determination of the boiling range distribution of petroleum products. This test method is applicable to petroleum distillates having an initial boiling point greater than 100 °C and a final boiling point less than 615 °C at atmospheric pressure as measured by this test method.  
1.2 The test method is not applicable for analysis of petroleum distillates 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. See Test Methods D7096, D2887, D6352, or D7169.  
1.3 This test method uses the principles of simulated distillation methodology.  
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.5 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, health, and environmental practices and determine the applicability of regulatory limitations prior to use.  
1.6 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

General Information

• Status: Published
• Publication Date: 31-Oct-2023
• ICS: 75.080 - Petroleum products in general
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.04.0H - Chromatographic Distribution Methods

Relations

• Replaces: ASTM D7213-15(2019) - Standard Test Method for Boiling Range Distribution of Petroleum Distillates in the Boiling Range from 100 °C to 615 °C by Gas Chromatography
• Effective Date: 01-Nov-2023
• Refers: ASTM D86-23ae1 - Standard Test Method for Distillation of Petroleum Products and Liquid Fuels at Atmospheric Pressure
• Effective Date: 01-Dec-2023
• Refers: ASTM D86-23a - Standard Test Method for Distillation of Petroleum Products and Liquid Fuels at Atmospheric Pressure
• Effective Date: 01-Dec-2023
• Refers: ASTM D2887-23 - Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography
• Effective Date: 01-Jul-2023
• Refers: ASTM D86-23 - Standard Test Method for Distillation of Petroleum Products and Liquid Fuels at Atmospheric Pressure
• Effective Date: 01-Mar-2023
• Refers: ASTM D2887-22e1 - Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography
• Effective Date: 01-Sep-2022
• Referred By: ASTM D7398-23 - Standard Test Method for Boiling Range Distribution of Fatty Acid Methyl Esters (FAME) in the Boiling Range from 100 °C to 615 °C by Gas Chromatography
• Effective Date: 01-Nov-2023
• Referred By: ASTM D7500-15(2019) - Standard Test Method for Determination of Boiling Range Distribution of Distillates and Lubricating Base Oils—in Boiling Range from 100 °C to 735 °C by Gas Chromatography
• Effective Date: 01-Nov-2023
• Referred By: ASTM D8519-23 - Standard Test Method for Determination of Hydrocarbon Types in Waste Plastic Process Oil Using Gas Chromatography with Vacuum Ultraviolet Absorption Spectroscopy Detection (GC-VUV)
• Effective Date: 01-Nov-2023

Overview

ASTM D7213-23 outlines the Standard Test Method for Boiling Range Distribution of Petroleum Distillates with initial boiling points above 100 °C and final boiling points below 615 °C, using gas chromatography. Developed by ASTM International, this method provides a simulated distillation procedure for determining the boiling point distribution of light and medium petroleum distillate fractions, offering a modern alternative to classical distillation methods in refinery and laboratory environments.

This test is applicable to petroleum products excluding low molecular weight materials such as naphtha, reformates, gasolines, and crude oils, as well as samples with non-hydrocarbon or residue components. Results from this method closely mirror those from true boiling point (TBP) distillation, enabling precise control and specification testing in petroleum refining.

Key Topics

• Boiling Range Distribution: Determines the profile of component boiling points for distillates between 100 °C and 615 °C, providing critical insight into sample composition.
• Gas Chromatography Methodology: Simulates atmospheric distillation using non-polar, high-temperature-stable open tubular capillary columns and flame ionization detection.
• Product Specification and Refining Control: Facilitates quality control, blending, and process optimization by replacing conventional distillation with automated, reproducible gas chromatographic analysis.
• Comparative Scope: Extends analytical coverage beyond ASTM D2887 (up to 538 °C) and below ASTM D6352 (up to 700 °C) to occupy a key range in petroleum product analysis.
• Calibration and Data Handling: Relies on calibration with known n-paraffins and uses area slice integration to develop detailed boiling range distribution tables.
• Measurement Units: All data are reported in SI units, consistent with international standards for laboratory testing.

Applications

ASTM D7213-23 is widely adopted in the petroleum industry for:

• Refinery Process Monitoring: Used to understand feedstock composition and adjust refining parameters, ensuring optimal yield and efficiency.
• Product Quality Certification: Supports product specification testing for light and medium distillate fractions, critical for compliance with commercial and regulatory standards.
• Research and Development: Enables rapid, accurate assessment of new formulations or process variations.
• Cross-Laboratory Consistency: Provides a robust standard for boiling range distribution results, minimizing variability and supporting global trade and quality assurance.

Industries benefit from faster analysis turnarounds, improved data reliability, and more comprehensive insight into product composition compared to traditional distillation procedures.

Related Standards

ASTM D7213-23 is part of a suite of petroleum test methods, each optimized for specific product ranges or sample types. Related standards include:

• ASTM D86 – Distillation of Petroleum Products and Liquid Fuels at Atmospheric Pressure
• ASTM D2887 – Boiling Range Distribution of Petroleum Fractions by Gas Chromatography (up to 538 °C)
• ASTM D2892 – True Boiling Point Distillation of Crude Petroleum
• ASTM D6352 – Gas Chromatography Boiling Range Distribution up to 700 °C
• ASTM D7096 – Boiling Range Distribution of Gasoline by Wide-Bore Capillary GC
• ASTM D7169 – Boiling Point Distribution for Residues and Crude Oils by High Temperature GC
• ASTM E355, E594, E1510 – Practices covering chromatographic terminology, detector testing, and capillary column installation

ASTM D7213-23 ensures method consistency, supports international trade, and fosters process optimization in petroleum product analysis through the use of advanced chromatographic techniques for boiling range determination.

Standards Content (Sample)

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D7213 − 23
Standard Test Method for
Boiling Range Distribution of Petroleum Distillates in the
Boiling Range from 100 °C to 615 °C by Gas
Chromatography
This standard is issued under the fixed designation D7213; 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* 2. Referenced Documents
2.1 ASTM Standards:
1.1 This test method covers the determination of the boiling
range distribution of petroleum products. This test method is D86 Test Method for Distillation of Petroleum Products and
Liquid Fuels at Atmospheric Pressure
applicable to petroleum distillates having an initial boiling
point greater than 100 °C and a final boiling point less than D1160 Test Method for Distillation of Petroleum Products at
Reduced Pressure
615 °C at atmospheric pressure as measured by this test
method. D2887 Test Method for Boiling Range Distribution of Pe-
troleum Fractions by Gas Chromatography
1.2 The test method is not applicable for analysis of
D2892 Test Method for Distillation of Crude Petroleum
petroleum distillates containing low molecular weight compo-
(15-Theoretical Plate Column)
nents (for example, naphthas, reformates, gasolines, crude
D4626 Practice for Calculation of Gas Chromatographic
oils). Materials containing heterogeneous components (for
Response Factors
example, alcohols, ethers, acids or esters) or residue are not to
D6352 Test Method for Boiling Range Distribution of Pe-
be analyzed by this test method. See Test Methods D7096,
troleum Distillates in Boiling Range from 174 °C to
D2887, D6352, or D7169.
700 °C by Gas Chromatography
1.3 This test method uses the principles of simulated distil-
D7096 Test Method for Determination of the Boiling Range
lation methodology.
Distribution of Gasoline by Wide-Bore Capillary Gas
Chromatography
1.4 The values stated in SI units are to be regarded as
D7169 Test Method for Boiling Point Distribution of
standard. No other units of measurement are included in this
Samples with Residues Such as Crude Oils and Atmo-
standard.
spheric and Vacuum Residues by High Temperature Gas
1.5 This standard does not purport to address all of the
Chromatography
safety concerns, if any, associated with its use. It is the
E355 Practice for Gas Chromatography Terms and Relation-
responsibility of the user of this standard to establish appro-
ships
priate safety, health, and environmental practices and deter-
E594 Practice for Testing Flame Ionization Detectors Used
mine the applicability of regulatory limitations prior to use.
in Gas or Supercritical Fluid Chromatography
1.6 This international standard was developed in accor-
E1510 Practice for Installing Fused Silica Open Tubular
dance with internationally recognized principles on standard-
Capillary Columns in Gas Chromatographs
ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom-
3. Terminology
mendations issued by the World Trade Organization Technical
3.1 Definitions—This test method makes reference to many
Barriers to Trade (TBT) Committee.
common gas chromatographic procedures, terms, and relation-
ships. Detailed definitions of these can be found in Practices
E355, E594, and E1510.
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
Subcommittee D02.04.0H on Chromatographic Distribution Methods. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Nov. 1, 2023. Published November 2023. Originally contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
approved in 2005. Last previous edition approved in 2019 as D7213 – 15 (2019). Standards volume information, refer to the standard’s Document Summary page on
DOI: 10.1520/D7213-23. 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
D7213 − 23
3.2 Definitions of Terms Specific to This Standard: tion detector. The detector signal integral is recorded as area
3.2.1 area slice, n—the area, resulting from the integration slices for consecutive retention time intervals during the
analysis.
of the chromatographic detector signal, within a specified
retention time interval. In area slice mode (see 6.4.2), peak
4.4 Retention times of known normal paraffin hydrocarbons
detection parameters are bypassed and the detector signal
spanning the scope of this test method (C -C ) are determined
5 60
integral is recorded as area slices of consecutive, fixed duration
and correlated to their boiling point temperatures. The normal-
time intervals.
ized cumulative corrected sample areas for each consecutive
3.2.2 corrected area slice, n—an area slice corrected for recorded time interval are used to calculate the boiling range
baseline offset, by subtraction of the exactly corresponding distribution. The boiling point temperature at each reported
area slice in a previously recorded blank (non-sample) analy- percent off increment is calculated from the retention time
sis. calibration.
3.2.3 cumulative corrected area, n—the accumulated sum of
5. Significance and Use
corrected area slices from the beginning of the analysis through
5.1 The boiling range distribution of light and medium
a given retention time, ignoring any non-sample area (for
petroleum distillate fractions provides an insight into the
example, solvent).
composition of feed stocks and products related to petroleum
3.2.4 final boiling point (FBP), n—the temperature (corre-
refining process, This gas chromatographic determination of
sponding to the retention time) at which a cumulative corrected
boiling range can be used to replace conventional distillation
area count equal to 99.5 % of the total sample area under the
methods for control of refining operations. This test method
chromatogram is obtained.
can be used for product specification testing with the mutual
3.2.5 initial boiling point (IBP), n—the temperature (corre- agreement of interested parties.
sponding to the retention time) at which a cumulative corrected
5.2 This test method extends the scope of boiling range
area count equal to 0.5 % of the total sample area under the
determination by gas chromatography to include light and
chromatogram is obtained.
medium petroleum distillate fractions beyond the scope of Test
3.2.6 slice rate, n—the time interval used to integrate the
Method D2887 (538 °C) and below Test Method D6352
continuous (analog) chromatographic detector response during (700 °C).
an analysis. The slice rate is expressed in Hz (for example,
5.3 Boiling range distributions obtained by this test method
integrations or slices per second).
are theoretically equivalent to those obtained by true boiling
3.2.7 slice time, n—the cumulative slice rate (analysis time)
point (TBP) distillation (see Test Method D2892). They are not
associated with each area slice throughout the chromatographic
equivalent to results from low efficiency distillation such as
analysis. The slice time is the time at the end of each those obtained with Test Method D86 or D1160.
contiguous area slice.
6. Apparatus
3.2.8 total sample area, n—the cumulative corrected area,
6.1 Chromatograph—The gas chromatographic system used
from the initial point to the final area point.
shall have the following performance characteristics:
3.3 Abbreviations—A common abbreviation of hydrocarbon
6.1.1 Column Oven—Capable of sustained and linear pro-
compounds is to designate the number of carbon atoms in the
grammed temperature operation from near ambient (for
compound. A prefix is used to indicate the carbon chain form,
example, 35 °C to 50 °C) up to 400 °C.
while a subscripted suffix denotes the number of carbon atoms
6.1.2 Column Temperature Programmer—The chromato-
(for example, normal decane n-C ; iso-tetradecane = i-C ).
l0 l4
graph shall be capable of linear programmed temperature
operation up to 400 °C at selectable linear rates up to
4. Summary of Test Method
20 °C ⁄min. The programming rate shall be sufficiently repro-
ducible to obtain the retention time repeatability of 0.1 min
4.1 The boiling range distribution by distillation is simu-
(6 s) for each component in the calibration mixture described
lated by the use of gas chromatography. The solvent should not
in 7.5.
interfere with measurement of the sample in the 100 °C to
6.1.3 Detector—This test method requires a flame ioniza-
615 °C range, and it should be apolar. A non-polar open tubular
tion detector (FID). The detector shall meet or exceed the
(capillary) gas chromatographic column is used to elute the
following specifications as detailed in Practice E594. The
hydrocarbon components of the sample in order of increasing
flame jet should have an orifice of approximately 0.45 mm to
boiling point.
0.50 mm.
4.2 A sample aliquot is diluted with a viscosity reducing
6.1.3.1 Operating Temperature, 400 °C.
solvent and introduced into the chromatographic system.
6.1.3.2 Sensitivity, >0.005 coulombs/g carbon.
Sample vaporization is provided by separate heating of the
-11
6.1.3.3 Minimum Detectability, 1 × 10 g carbon/s.
point of injection or in conjunction with column oven heating. 6
6.1.3.4 Linear Range, >10 .
4.3 The column oven temperature is raised at a reproducible 6.1.3.5 Connection of the column to the detector shall be
linear rate to effect separation of the hydrocarbon components such that no temperature below the column temperature exists.
in order of increasing boiling point. The elution of sample Refer to Practice E1510 for proper installation and condition-
components is quantitatively determined using a flame ioniza- ing of the capillary column.
D7213 − 23
6.1.4 Sample Inlet System—Any sample inlet system ca- 7. Reagents and Materials
pable of meeting the performance specification in 7.6 may be
7.1 Carrier Gas—Helium or hydrogen of high purity.
used. Programmed temperature vaporization (PTV) and pro-
(Warning—Helium and hydrogen are compressed gases under
grammable cool on-column injection systems have been used
high pressure; hydrogen is an extremely flammable gas under
successfully.
high pressure.) These gases may be used as the carrier gas and
6.1.5 Carrier Gas Flow Control—The chromatograph shall
should not contain more than 5 mL/m of oxygen. The total
be equipped with carrier gas pressure or flow control capable of
amount of impurities should not exceed 10 mL/m . Additional
maintaining constant carrier gas flow control through the
purification is recommended by the use of molecular sieves or
column throughout the column temperature program cycle.
other suitable agents to remove water, oxygen, and hydrocar-
bons. Available pressure shall be sufficient to ensure a constant
6.2 Microsyringe—A microsyringe with a 23 gauge or
carrier gas flow rate.
smaller stainless steel needle is used for on-column sample
7.2 Hydrogen—Hydrogen of high purity (for example,
introduction. Syringes of 0.1 μL to 10 μL capacity are avail-
hydrocarbon-free) is used as fuel for the flame ionization
able.
detector (FID). (Warning—Hydrogen is an extremely flam-
6.2.1 Automatic syringe injection is recommended to
mable gas under high pressure.)
achieve best precision.
7.3 Air—High purity (for example, hydrocarbon-free) com-
6.3 Column—This test method is limited to the use of
pressed air is used as the oxidant for the flame ionization
non-polar wall coated open tubular (WCOT) columns of high
detector (FID). (Warning—Compressed air is a gas under high
thermal stability. Glass, fused silica, and stainless steel
pressure and supports combustion.)
columns, with a 0.53 mm diameter have been successfully
7.4 Solvents—Unless otherwise indicated, it is intended that
used. Cross-linked or bonded 100 % dimethyl-polysiloxane
all solvents conform to the specifications of the committee on
stationary phases with film thickness of 0.5 μm to 1.0 μm have
analytical Reagents of the American Chemical Society where
been used. The column length and liquid phase film thickness
such specifications are available. Other grades may be used
shall allow the elution of at least C n-paraffin (BP = 615 °C).
provided it is first ascertained that the solvent is of sufficiently
The column and conditions shall provide separation of typical
high purity to permit its use without lessening the accuracy of
petroleum hydrocarbons in order of increasing boiling point
the determination.
and meet the column resolution requirements of 8.2.1. The
7.4.1 Carbon Disulfide (CS )—(99+ % pure) may be used as
column shall provide a resolution between one and ten using 2
a viscosity reducing solvent and as a means of reducing mass
this test method’s operating conditions.
of sample introduced onto the column to ensure linear detector
6.4 Data Acquisition System:
response and reduced peak skewness. It is miscible with
6.4.1 Recorder—A 0 mV to 1 mV range recording potenti-
asphaltic hydrocarbons and provides a relatively small re-
ometer or equivalent, with a full-scale response time of 2 s or
sponse with the FID. The quality (hydrocarbon content) should
less may be used to provide a graphical display. be determined by this test method prior to use as a sample
diluent. (Warning—Carbon disulfide is extremely flammable
6.4.2 Integrator—Means shall be provided for determining
and toxic.)
the accumulated area under the chromatogram. This can be
done by means of an electronic integrator or computer-based
7.5 Cyclohexane (C H )—(99+ % pure) may be used as a
6 12
chromatography data system. The integrator/computer system
viscosity reducing solvent. It is miscible with asphaltic
shall have normal chromatographic software for measuring the
hydrocarbons, however, it responds well to the FID. The
retention time and areas of eluting peaks (peak detection
quality (hydrocarbon content) should be determined by this test
mode). In addition, the system shall be capable of converting
method prior to use as a sample diluent. (Warning—
the continuously integrated detector signal into area slices of
Cyclohexane is flammable.)
fixed duration (area slice mode). These contiguous area slices,
7.6 Calibration Mixture—A qualitative mixture of
collected for the entire analysis, are stored for later processing.
n-paraffins (nominally C to C ) dissolved in a suitable
5 60
The electronic range of the integrator/computer (for example, 1
solvent. The final concentration should be approximately one
V, 10 V) shall be operated within the linear range of the
part of n-paraffin mixture to one hundred parts of solvent. At
detector/electrometer system used.
NOTE 1—Some gas chromatographs have an algorithm built into their
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
operating software that allows a mathematical model of the baseline
Standard-Grade Reference Materials, American Chemical Society, Washington,
profile to be stored in memory. This profile is automatically subtracted
DC. For suggestions on the testing of reagents not listed by the American Chemical
from the detector signal on subsequent sample runs to compensate for the
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
column bleed. Some integration systems also store and automatically U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
subtract a blank analysis from subsequent analytical determinations. copeial Convention, Inc. (USPC), Rockville, MD.
D7213 − 23
least one compound in the mixture shall have a boiling point (or a polywax retention time boiling point mixture) (see 7.6).
lower than the initial boiling point of the sample being Resolution (R) should be at least one and not more than ten,
analyzed, as defined in the scope of this test method (1.1). The using the identical conditions employed for sample analyses.
calibration mixture shall contain at least 13 known n-paraffins
R 5 2 t 2 t / 1.699 w 1w (1)
~ ! ~ ~ !!
2 1 2 1
(for example, C , C , C , C , C , C , C , C , C , C , C ,
6 7 8 9 10 12 16 20 30 40 50
where:
C , C ). Boiling points of n-paraffins are listed in Table 1.
52 60
R = resolution,
NOTE 2—A suitable calibration mixture can be obtained by dissolving
4 t = time for the n-C peak maximum,
1 50
a polyolefin wax (for example, Polywax 500 ) in a volatile solvent (for
t = time for the n-C peak maximum,
example, carbon disulfide or cyclohexane). Solutions of one part Polywax 2 52
w = peak width, at half height, of the n-C peak and,
to one hundred parts solvent can be prepared. Lower boiling point 1 50
paraffins will have to be added to insure conformance with 7.6. Fig. 1 w = peak width, at half height, of the n-C peak.
2 52
illustrates a typical calibration mixture chromatogram.
8.2.2 Detector Response Calibration—This test method as-
7.7 Response Linearity Mixture—Prepare a quantitatively
sumes that the FID response to petroleum hydrocarbons is
weighed mixture of at least ten individual paraffins (>99 %
proportional to the mass of individual components. This shall
purity), covering the boiling range of the test method. The
be verified when the system is put in service, and whenever any
highest boiling point component should be at least n-C . The
changes are made to the system or operational parameters.
mixture shall contain n-C . Use a suitable solvent to provide
Analyze the response linearity mixture (see 7.7) using the
a solution of each component at approximately 0.5 % to 2.0 %
identical procedure to be used for the analysis of samples (see
by mass.
Section 9). Calculate the relative response factor for each
7.8 Reference Material—A reference sample that has been n-paraffin (relative to n-tetracontane) as per Practice D4626
and Eq 2:
analyzed by laboratories participating in the test method
cooperative study. Consensus values for the boiling range
F 5 M /A / M /A (2)
~ ! ~ !
n n n 40 40
distribution of this sample are being determined.
where:
8. Preparation of Apparatus F = relative response factor,
n
M = mass of the n-paraffin in the mixture,
n
8.1 Gas Chromatograph Setup:
A = peak area of the n-paraffin in the mixture,
n
8.1.1 Place the gas chromatograph and ancillary equipment
M = mass of the n-tetracontane in the mixture, and
into operation in accordance with the manufacturers instruc-
A = peak area of the n-tetracontane in the mixture.
tions. Recommended operating conditions are shown in Table
8.2.2.1 The relative response factor (F ) of each n-paraffin
2. n
shall not deviate from unity by more than 65 %.
8.1.2 When attaching the column to the detector inlet,
8.2.3 Column Temperature—The column temperature pro-
ensure that the end of the column terminates as close as
gram profile is selected such that the C peak can be differen-
possible to the FID jet. Follow the instructions in Practice 5
tiated from the solvent and that the maximum boiling point
E1510.
(615 °C) n-paraffin (C ) is eluted from the column before
8.1.3 The FID should be periodically inspected and, if 60
reaching the end of the temperature program. The actual
necessary, remove any foreign deposits formed in the detector
program rate used will be influenced by other operating
from combustion of silicone liquid phase or other materials.
variables such as column dimensions, liquid phase film
Such deposits will change the response characteristics of the
thickness, carrier gas and flow rate, and sample size.
detector.
8.2.4 Column Elution Characteristics—The recommended
8.1.4 The inlet liner and initial portion of the column shall
column liquid phase is a non-polar phase such as 100 %
be periodically inspected and replaced if necessary to remove
dimethyl-polysiloxane.
extraneous deposits or sample residue.
8.1.5 Column Conditioning—A new column will require
9. Procedure
conditioning at the upper test method operating temperature to
reduce or eliminate significant liquid phase bleed, resulting in
9.1 Analysis Sequence Protocol—Define and use a predeter-
a stable chromatographic baseline. Follow the guidelines
mined schedule of analysis events designed to achieve maxi-
outlined in Practice E1510.
mum reproducibility for these determinations. The schedule
will include cooling the column oven and injector to the initial
8.2 System Performance Specification:
8.2.1 Column Resolution—The column resolution, influ- starting temperature, equilibration time, sample injection and
system start, analysis, and final temperature hold time.
enced by both the column physical parameters and operating
conditions, affects the overall determination of boiling range 9.1.1 After chromatographic conditions have been set to
distribution. Resolution is therefore specified to maintain meet performance requirements, program the column tempera-
equivalence between different systems (laboratories) employ- ture upward to the maximum temperature to be used and hold
ing this test method. Resolution is determined using Eq 1 and that temperature for the selected time. Following the analysis
the C and C paraffins from a calibration mixture analysis sequence protocol, cool the column to the initial starting
50 52
temperature.
9.1.2 During the cool down and equilibration time, ready
Polywax is a trademark of the Baker Petrolite Corporation, Barnsdall, OK. the integrator/computer system. If a retention time calibration
D7213 − 23
A,B
TABLE 1 Boiling Points of n-Paraffins
Carbon Boiling Boiling
Number Point °C Point °F
5 36 97
6 69 156
7 98 209
8 126 258
9 151 303
10 174 345
11 196 385
12 216 421
13 235 456
14 254 488
15 271 519
16 287 548
17 302 576
18 316 601
19 330 626
20 344 651
21 356 674
22 369 695
23 380 716
24 391 736
25 402 755
26 412 774
27 422 791
28 431 808
29 440 825
30 449 840
31 458 856
32 466 870
33 474 885
34 481 898
35 489 912
36 496 925
37 503 937
38 509 948
39 516 961
40 522 972
41 528 982
42 534 993
43 540 1004
44 545 1013
45 550 1022
46 556 1033
47 561 1042
48 566 1051
49 570 1058
50 575 1067
51 579 1074
52 584 1083
53 588 1090
54 592 1098
55 596 1105
56 600 1112
57 604 1119
58 608 1126
59 612 1134
60 615 1139
A
API Project 44, 72-10-31, is believed to have provided the original normal paraffin boiling point data that are listed in Table 1. However, over the years some of the data
contained in both API Project 44 (Thermodynamics Research Center Hydrocarbon Project) and Test Method D7213 have changed, and they are no longer equivalent. Table
1 represents the current normal paraffin boiling point values accepted by Subcommittee D02.04 and found in all test methods under the jurisdiction of Section D02.04.H.
B
Test Method D7213 has traditionally used n-paraffin boiling points rounded to the nearest whole degree for calibration. The boiling points listed in Table 1 are correct to
the nearest whole number in both degrees Celsius and degrees Fahrenheit. However, if a conversion is made from one unit to the other and then rounded to a whole
number, the results will not agree with the table values for a few carbon numbers. For example, the boiling point of n-heptane is 98.425 °C which is correctly rounded to
98 °C in the table. However, converting 98.425 °C gives 209.165 °F, which rounds to 209 °F, while converting 98 °C gives 208.4 °F, which rounds to 208 °F. Carbon
numbers 2, 4, 7, 8, 9, 13, 14, 15, 16, 25, 27, and 32 are affected by rounding.
D7213 − 23
FIG. 1 Typical Calibration Curve with Plot
is being performed, use the peak detection mode. For samples or make no injection (baseline blank). At the time of injection,
and baseline compensation (with or without solvent injection),
start the chromatograph time cycle and the integrator/computer
use the area slice mode operation. The recommended slice rate
data acquisition. Follow the analysis protocol for all subse-
for this test method is 1.0 Hz (3.3 slices per second). Other
quent repetitive analyses or calibrations. Since complete reso-
slice rates may be used if within the limits of 0.02 % and 0.2 %
lution of sample peaks is not expected, do not change the
of the retention time of the final calibration component (C ).
sensitivity setting during the analysis.
Faster slice rates may be used, as may be required for other
9.2 Baseline Blank—Perform a blank analysis (baseline
reasons, if provision is made to accumulate (bunch) the slice
blank) at least once per day. The blank analysis may be without
data to within these limits prior to determination of the boiling
injection or by injection of an equivalent solvent volume as
range distribution.
used with sample injections, depending upon the subsequent
9.1.3 At the exact time set by the schedule, inject either the
calibration mixture, solvent, or sample into the chromatograph; data handling capabilities for baseline/solvent compensation.
D7213 − 23
A
TABLE 2 Recommended Operating Conditions
Injector Cool on-column. Temperature Programmable Inlet (no Split)
Injection temperature Oven-track mode
Auto sampler Required for best precision
Data collection Data is collected as independent area slices
(average data collection rate is 1.0 Hz or
3.3 slices per second)
Column Capillary, 5 m by 0.53 mm id
film thickness; 0.1 μm to 1.0 μm (polymethylsiloxane) 0.8 μm – 1.0 μm
was used in the ILS study
Flow conditions UHP helium at 12 mL/min (constant flow)
Carrier: He and Hydrogen were used in the ILS Study (make-up gas helium at 18 mL/min)
Detector Flame Ionization;
Temperature: 390 °C
Oven program Initial oven temperature 35 °C – 50 °C,
initial hold 0 min,
program rate 10 °C/min.,
final oven temperature 380 °C,
final hold 12 min,
equilibration time 2 min
Sample size 1 μL
Sample dilution 2 mass percent in carbon disulfide
Calibration dilution 1 mass percent in carbon disulfide
A
Hydrogen was used in the precision study. Results were found to be “statistically equivalent.” See Research Report RR:D02-1725.
The blank analysis is typically performed prior to sample 9.3.1.1 Skewness Calculation—Calculate the ratio A/B on
analyses, but may be useful if determined between samples or specified peaks in the calibration mixture as indicated by the
at the end of a sample sequence to provide additional data designations in Fig. 2. A is the width in seconds of the portion
regarding instrument operation or residual sample carryover of the peak eluting prior to the time of the peak apex and
from previous sample analyses. measured at 10 % of peak height (0.10-H), and B is the width
NOTE 3—If automatic baseline correction (see Note 1) is provided by
in seconds of the portion of the peak eluting after the time of
the gas chromatograph, further correction of area slices may not be
the peak apex at 10 % of peak height (0.10-H). This ratio for
required. However, if an electronic offset is added to the signal after
n-pentacontane (n-C ) peak in
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM 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.
Designation: D7213 − 15 (Reapproved 2019) D7213 − 23
Standard Test Method for
Boiling Range Distribution of Petroleum Distillates in the
Boiling Range from 100 °C to 615 °C by Gas
Chromatography
This standard is issued under the fixed designation D7213; 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 Scope*
1.1 This test method covers the determination of the boiling range distribution of petroleum products. This test method is
applicable to petroleum distillates having an initial boiling point greater than 100 °C and a final boiling point less than 615 °C at
atmospheric pressure as measured by this test method.
1.2 The test method is not applicable for analysis of petroleum distillates 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. See Test Methods D7096, D2887, D6352, or D7169.
1.3 This test method uses the principles of simulated distillation methodology.
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.5 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, health, and environmental practices and determine the applicability of
regulatory limitations prior to use.
1.6 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ASTM Standards:
D86 Test Method for Distillation of Petroleum Products and Liquid Fuels at Atmospheric Pressure
D1160 Test Method for Distillation of Petroleum Products at Reduced Pressure
D2887 Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography
D2892 Test Method for Distillation of Crude Petroleum (15-Theoretical Plate Column)
D4626 Practice for Calculation of Gas Chromatographic Response Factors
This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of Subcommittee
D02.04.0H on Chromatographic Distribution Methods.
Current edition approved Dec. 1, 2019Nov. 1, 2023. Published December 2019November 2023. Originally approved in 2005. Last previous edition approved in 20152019
as D7213 – 15.D7213 – 15 (2019). DOI: 10.1520/D7213-15R19.10.1520/D7213-23.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. 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
D7213 − 23
D6352 Test Method for Boiling Range Distribution of Petroleum Distillates in Boiling Range from 174 °C to 700 °C by Gas
Chromatography
D7096 Test Method for Determination of the Boiling Range Distribution of Gasoline by Wide-Bore Capillary Gas
Chromatography
D7169 Test Method for Boiling Point Distribution of Samples with Residues Such as Crude Oils and Atmospheric and Vacuum
Residues by High Temperature Gas Chromatography
E355 Practice for Gas Chromatography Terms and Relationships
E594 Practice for Testing Flame Ionization Detectors Used in Gas or Supercritical Fluid Chromatography
E1510 Practice for Installing Fused Silica Open Tubular Capillary Columns in Gas Chromatographs
3. Terminology
3.1 Definitions—This test method makes reference to many common gas chromatographic procedures, terms, and relationships.
Detailed definitions of these can be found in Practices E355, E594, and E1510.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 area slice, n—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, n—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, n—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).
3.2.4 final boiling point (FBP), n—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), n—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, n—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, n—the cumulative slice rate (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, n—the cumulative corrected area, from the initial point to the final area point.
3.3 Abbreviations—A common abbreviation of hydrocarbon compounds is to designate the number of carbon atoms in the
compound. A prefix is used to indicate the carbon chain form, while a subscripted suffix denotes the number of carbon atoms (for
example, normal decane n-C ; iso-tetradecane = i-C ).
l0 l4
4. Summary of Test Method
4.1 The boiling range distribution by distillation is simulated by the use of gas chromatography. The solvent should not interfere
with measurement of the sample in the 100 °C to 615 °C range, and it should be apolar. A non-polar open tubular (capillary) gas
chromatographic column is used to elute the hydrocarbon components of the sample in order of increasing boiling point.
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 reproducible linear rate to effect separation of the hydrocarbon components in order
D7213 − 23
of increasing boiling point. The elution of sample components is quantitatively determined using a flame ionization detector. The
detector signal integral 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 this test method (C -C ) are determined and
5 60
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 light and medium petroleum distillate fractions provides an insight into the composition of
feed stocks and products related to petroleum refining process, This gas chromatographic determination of boiling range 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 light and medium
petroleum distillate fractions beyond the scope of Test Method D2887 (538 °C) and below Test Method D6352 (700 °C).
5.3 Boiling range distributions obtained by this test method are theoretically equivalent to those obtained by true boiling point
(TBP) distillation (see Test Method D2892). They are not equivalent to results from low efficiency distillation such as those
obtained with Test Method D86 or D1160.
6. Apparatus
6.1 Chromatograph—The gas chromatographic system used shall have the following performance characteristics:
6.1.1 Column Oven—Capable of sustained and linear programmed temperature operation from near ambient (for example, 35 °C
to 50 °C) up to 400 °C.
6.1.2 Column Temperature Programmer—The chromatograph shall be capable of linear programmed temperature operation up to
400 °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.
6.1.3 Detector—This test method requires a flame ionization detector (FID). The detector shall meet or exceed the following
specifications as detailed in Practice E594. The flame jet should have an orifice of approximately 0.45 mm to 0.50 mm.
6.1.3.1 Operating Temperature, 400 °C.
6.1.3.2 Sensitivity, >0.005 coulombs/g carbon.
-11
6.1.3.3 Minimum Detectability, 1 × 10 g carbon/s.
6.1.3.4 Linear Range, >10 .
6.1.3.5 Connection of the column to the detector shall be such that no temperature below the column temperature exists. Refer
to Practice E1510 for proper installation and conditioning of the capillary column.
6.1.4 Sample Inlet System—Any sample inlet system capable of meeting the performance specification in 7.6 may be used.
Programmed temperature vaporization (PTV) and programmable cool on-column injection systems have been used successfully.
6.1.5 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.
6.2 Microsyringe—A microsyringe with a 23 gauge or smaller stainless steel needle is used for on-column sample introduction.
Syringes of 0.1 μL to 10 μL capacity are available.
6.2.1 Automatic syringe injection is recommended to achieve best precision.
D7213 − 23
6.3 Column—This test method is limited to the use of non-polar wall coated open tubular (WCOT) columns of high thermal
stability. Glass, fused silica, and stainless steel columns, with a 0.53 mm diameter have been successfully used. Cross-linked or
bonded 100 % dimethyl-polysiloxane stationary phases with film thickness of 0.5 μm to 1.0 μm have been used. The column length
and liquid phase film thickness shall allow the elution of at least C n-paraffin (BP = 615 °C). The column and conditions shall
provide separation of typical petroleum hydrocarbons in order of increasing boiling point and meet the column resolution
requirements of 8.2.1. The column shall provide a resolution between one and ten using this test method’s operating conditions.
6.4 Data Acquisition System:
6.4.1 Recorder—A 0 mV to 1 mV range recording potentiometer or equivalent, with a full-scale response time of 2 s or less may
be used to provide a graphical display.
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 (area slice
mode). 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 1—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 or hydrogen of high purity. (Warning—Helium and hydrogen are compressed gases under high
pressure; hydrogen is an extremely flammable gas under high pressure.) These gases may be used as the carrier gas and should
3 3
not contain more than 5 mL/m of oxygen. The total amount of impurities should not exceed 10 mL/m . 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 flame ionization detector (FID).
(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 flame ionization detector (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) may be 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 quality (hydrocarbon content) should be determined by
this test method prior to use as a sample diluent. (Warning—Carbon disulfide is extremely flammable and toxic.)
7.5 Cyclohexane (C H )—(99+ % pure) may be used as a viscosity reducing solvent. It is miscible with asphaltic hydrocarbons,
6 12
however, it responds well to the FID. The quality (hydrocarbon content) should be determined by this test method prior to use as
a sample diluent. (Warning—Cyclohexane is flammable.)
7.6 Calibration Mixture—A qualitative mixture of n-paraffins (nominally C to C ) dissolved in a suitable solvent. The final
5 60
ACS Reagent Chemicals, Specifications and Procedures for Reagents and Standard-Grade Reference Materials, American Chemical Society, Washington, DC. For
suggestions on the testing of reagents not listed by the American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and
the United States Pharmacopeia and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
D7213 − 23
concentration should be approximately one part of n-paraffin mixture to one hundred parts of solvent. At least one compound in
the mixture shall have a boiling point lower than the initial boiling point of the sample being analyzed, as defined in the scope of
this test method (1.1). The calibration mixture shall contain at least 13 known n-paraffins (for example, C , C , C , C , C , C ,
6 7 8 9 10 12
C , C , C , C , C , C , C ). Boiling points of n-paraffins are listed in Table 1.
16 20 30 40 50 52 60
NOTE 2—A suitable calibration mixture can be obtained by dissolving a polyolefin wax (for example, Polywax 500 ) in a volatile solvent (for example,
carbon disulfide or cyclohexane). Solutions of one part Polywax to one hundred parts solvent can be prepared. Lower boiling point paraffins will have
to be added to insure conformance with 7.6. Fig. 1 illustrates a typical calibration mixture chromatogram.
7.7 Response Linearity Mixture—Prepare a quantitatively weighed mixture of at least ten individual paraffins (>99 % purity),
covering the boiling range of the test method. The highest boiling point component should be at least n-C . The mixture shall
contain n-C . Use a suitable solvent to provide a solution of each component at approximately 0.5 % to 2.0 % by mass.
Polywax is a trademark of the Baker Petrolite Corporation, Barnsdall, OK.
D7213 − 23
A,B
TABLE 1 Boiling Points of n-Paraffins
Carbon Boiling Boiling
Number Point °C Point °F
5 36 97
6 69 156
7 98 209
8 126 258
9 151 303
10 174 345
11 196 385
12 216 421
13 235 456
14 254 488
15 271 519
16 287 548
17 302 576
18 316 601
19 330 626
20 344 651
21 356 674
22 369 695
23 380 716
24 391 736
25 402 755
26 412 774
27 422 791
28 431 808
29 440 825
30 449 840
31 458 856
32 466 870
33 474 885
34 481 898
35 489 912
36 496 925
37 503 937
38 509 948
39 516 961
40 522 972
41 528 982
42 534 993
43 540 1004
44 545 1013
45 550 1022
46 556 1033
47 561 1042
48 566 1051
49 570 1058
50 575 1067
51 579 1074
52 584 1083
53 588 1090
54 592 1098
55 596 1105
56 600 1112
57 604 1119
58 608 1126
59 612 1134
60 615 1139
A
API Project 44, 72-10-31, is believed to have provided the original normal paraffin boiling point data that are listed in Table 1. However, over the years some of the data
contained in both API Project 44 (Thermodynamics Research Center Hydrocarbon Project) and Test Method D7213 have changed, and they are no longer equivalent. Table
1 represents the current normal paraffin boiling point values accepted by Subcommittee D02.04 and found in all test methods under the jurisdiction of Section D02.04.H.
B
Test Method D7213 has traditionally used n-paraffin boiling points rounded to the nearest whole degree for calibration. The boiling points listed in Table 1 are correct to
the nearest whole number in both degrees Celsius and degrees Fahrenheit. However, if a conversion is made from one unit to the other and then rounded to a whole
number, the results will not agree with the table values for a few carbon numbers. For example, the boiling point of n-heptane is 98.425 °C which is correctly rounded to
98 °C in the table. However, converting 98.425 °C gives 209.165 °F, which rounds to 208 °F,209 °F, while converting 98 °C gives 208.4 °F, which rounds to 208 °F. Carbon
numbers 2, 4, 7, 8, 9, 13, 14, 15, 16, 25, 27, and 32 are affected by rounding.
D7213 − 23
FIG. 1 Typical Calibration Curve with Plot
7.8 Reference Material—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 being determined.
8. Preparation of Apparatus
8.1 Gas Chromatograph Setup:
8.1.1 Place the gas chromatograph and ancillary equipment into operation in accordance with the manufacturers instructions.
Recommended operating conditions are shown in Table 2.
D7213 − 23
A
TABLE 2 Recommended Operating Conditions
Injector Cool on-column. Temperature Programmable Inlet (no Split)
Injection temperature Oven-track mode
Auto sampler Required for best precision
Data collection Data is collected as independent area slices
(average data collection rate is 1.0 Hz or
3.3 slices per second)
Column Capillary, 5 m by 0.53 mm id
film thickness; 0.1 μm to 1.0 μm (polymethylsiloxane) 0.8 μm – 1.0 μm
was used in the ILS study
Flow conditions UHP helium at 12 mL/min (constant flow)
Carrier: He and Hydrogen were used in the ILS Study (make-up gas helium at 18 mL/min)
Detector Flame Ionization;
Temperature: 390 °C
Oven program Initial oven temperature 35 °C – 50 °C,
initial hold 0 min,
program rate 10 °C/min.,
final oven temperature 380 °C,
final hold 12 min,
equilibration time 2 min
Sample size 1 μL
Sample dilution 2 mass percent in carbon disulfide
Calibration dilution 1 mass percent in carbon disulfide
A
Hydrogen was used in the precision study. Results were found to be “statistically equivalent.” See Research Report RR:D02-1725.
8.1.2 When attaching the column to the detector inlet, ensure that the end of the column terminates as close as possible to the FID
jet. Follow the instructions in Practice E1510.
8.1.3 The FID should be periodically inspected and, if necessary, remove any foreign deposits formed in the detector from
combustion of silicone liquid phase or other materials. Such deposits will change the response characteristics of the detector.
8.1.4 The inlet liner and initial portion of the column shall be periodically inspected and replaced if necessary to remove
extraneous deposits or sample residue.
8.1.5 Column Conditioning—A new column will require conditioning at the upper test method operating temperature to reduce
or eliminate significant liquid phase bleed, resulting in a stable chromatographic baseline. Follow the guidelines outlined in
Practice E1510.
8.2 System Performance Specification:
8.2.1 Column Resolution—The column resolution, influenced by both the column physical parameters and operating conditions,
affects the overall determination of boiling range distribution. Resolution is therefore specified to maintain equivalence between
different systems (laboratories) employing this test method. Resolution is determined using Eq 1 and the C and C paraffins from
50 52
a calibration mixture analysis (or a polywax retention time boiling point mixture) (see 7.6). Resolution (R) should be at least one
and not more than ten, using the identical conditions employed for sample analyses.
R 5 2 t 2 t / 1.699 w 1w (1)
~ ! ~ ~ !!
2 1 2 1
where:
R = resolution,
t = time for the n-C peak maximum,
1 50
t = time for the n-C peak maximum,
2 52
w = peak width, at half height, of the n-C peak and,
1 50
w = peak width, at half height, of the n-C peak.
2 52
8.2.2 Detector Response Calibration—This test method assumes that the FID response to petroleum hydrocarbons is proportional
to the mass of individual components. This shall be verified when the system is put in service, and whenever any changes are made
to the system or operational parameters. Analyze the response linearity mixture (see 7.7) using the identical procedure to be used
for the analysis of samples (see Section 9). Calculate the relative response factor for each n-paraffin (relative to n-tetracontane)
as per Practice D4626 and Eq 2:
F 5 M /A / M /A (2)
~ ! ~ !
n n n 40 40
D7213 − 23
where:
F = relative response factor,
n
M = mass of the n-paraffin in the mixture,
n
A = peak area of the n-paraffin in the mixture,
n
M = mass of the n-tetracontane in the mixture, and
A = peak area of the n-tetracontane in the mixture.
8.2.2.1 The relative response factor (F ) of each n-paraffin shall not deviate from unity by more than 65 %.
n
8.2.3 Column Temperature—The column temperature program profile is selected such that the C peak can be differentiated from
the solvent and that the maximum boiling point (615 °C) n-paraffin (C ) is eluted from the column before reaching the end of the
temperature program. The actual program rate used will be influenced by other operating variables such as column dimensions,
liquid phase film thickness, carrier gas and flow rate, and sample size.
8.2.4 Column Elution Characteristics—The recommended column liquid phase is a non-polar phase such as 100 % dimethyl-
polysiloxane.
9. Procedure
9.1 Analysis Sequence Protocol—Define and use a predetermined schedule of analysis events designed to achieve maximum
reproducibility for these determinations. The schedule will include cooling the column oven and injector to the initial starting
temperature, equilibration time, sample injection and system start, analysis, and final temperature hold time.
9.1.1 After chromatographic conditions have been set to meet performance requirements, program the column temperature upward
to the maximum temperature to be used and hold that temperature for the selected time. Following the analysis sequence protocol,
cool the column to the initial starting temperature.
9.1.2 During the cool down and equilibration time, ready the integrator/computer system. If a retention time calibration is being
performed, use the peak detection mode. For samples and baseline compensation (with or without solvent injection), use the area
slice mode operation. The recommended slice rate for this test method is 1.0 Hz (3.3 slices per second). Other slice rates may be
used if within the limits of 0.02 % and 0.2 % of the retention time of the final calibration component (C ). Faster slice rates may
be used, as may be required for other reasons, if provision is made to accumulate (bunch) the slice data to within these limits prior
to determination of the boiling range distribution.
9.1.3 At the exact time set by the schedule, inject either the calibration mixture, solvent, or sample into the chromatograph; or
make no injection (baseline blank). At the time of injection, start the chromatograph time cycle and the integrator/computer data
acquisition. Follow the analysis protocol for all subsequent repetitive analyses or calibrations. Since complete resolution of sample
peaks is not expected, do not change the sensitivity setting during the analysis.
9.2 Baseline Blank—Perform a blank analysis (baseline blank) at least once per day. The blank analysis may be without injection
or by injection of an equivalent solvent volume as used with sample injections, depending upon the subsequent data handling
capabilities for baseline/solvent compensation. The blank analysis is typically performed prior to sample analyses, but may be
useful if determined between samples or at the end of a sample sequence to provide additional data regarding instrument operation
or residual sample carryover from previous sample analyses.
NOTE 3—If automatic baseline correction (see Note 1) is provided by the gas chromatograph, further correction of area slices may not be required.
However, if an electronic offset is added to the signal after baseline compensation, additional area slice correction may be required in the form of offset
subtraction. Consult the specific instrumentation instructions to determine if an offset is applied to the signal. If the algorithm used is unclear, the slice
area data can be examined to determine if further correction is necessary. Determine if any offset has been added to the compensated signal by examining
...