ASTM D7807-20

Standard Test Method for Determination of Boiling Range Distribution of Hydrocarbon and Sulfur Components of Petroleum Distillates by Gas Chromatography and Chemiluminescence Detection

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 processes. 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 Test Method D2887 (538 °C) boiling range determination by gas chromatography to include sulfur boiling range distribution in the petroleum distillate fractions. Knowledge of the amount of sulfur and its distribution in hydrocarbons is economically important in determining product value and in determining how best to process or refine intermediate products. Sulfur compounds are known to affect numerous properties of petroleum and petrochemical products. The corrosion of metals and poisoning of catalysts is of particular concern. In addition, the content of sulfur in various refined products may be subject to governmental regulations. Test Methods, such as, D2622, D3120, D5504 and D5623, are available to determine total sulfur content or content of individual sulfur compounds in petroleum and petroleum products. Test Methods, such as, D86, D1160, D2887, D3710, and D2892, are also available to determine the hydrocarbon boiling ranges of such samples. The gas chromatographic determination of the sulfur boiling range assists in process development, in treatment and control of refining operations and is useful for assessing product quality. This determination produces detailed information about the sulfur distribution in a sample that cannot be obtained by either total sulfur analysis or analysis of sulfur in discreet distillation cuts.  
5.2.1 The hydrocarbon boiling range distributions obtained by Test Method D2887 are theoretically equivalent to those obtained by true boiling...
SCOPE
1.1 This test method covers the determination of the boiling range distribution of petroleum products. The test method is applicable to petroleum products and fractions having a final boiling point of 538 °C (1000 °F) or lower at atmospheric pressure as measured by this test method. This test method is limited to samples having a boiling range greater than 55 °C (100 °F), and having a vapor pressure sufficiently low to permit sampling at ambient temperature.  
1.1.1 The applicable sulfur concentration range will vary to some extent depending on the boiling point distribution of the sample and the instrumentation used; however, in most cases, the test method is applicable to samples containing levels of sulfur above 10 mg/kg.  
1.2 This test method requires the use of both FID and SCD for detection. The hydrocarbon simulated distillation data obtained from the FID signal should be performed according to Test Method D2887 Procedure B.  
1.3 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 D3710, D7096, D5307, D7169, or D7500.  
1.4 This test method does not purport to identify all sulfur species in a sample. The detector response to sulfur is equimolar for all sulfur compounds within the scope (1.1) of this test method. Thus, unidentified sulfur compounds are determined with equal precision to that of identified substances. Total sulfur content is determined from the total area of the sulfur detector.  
1.4.1 This test method uses the principles of simulated distillation methodology.  
1.5 The values stated in SI units are to be regarded as standard. The values given in parentheses are for information only.  
1.6 This standard ...

General Information

• Status: Published
• Publication Date: 30-Apr-2020
• 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 D7807-12 - Standard Test Method for Determination of Boiling Range Distribution of Hydrocarbon and Sulfur Components of Petroleum Distillates by Gas Chromatography and Chemiluminescence Detection
• Effective Date: 01-May-2020
• Refers: ASTM D5623-24 - Standard Test Method for Sulfur Compounds in Light Petroleum Liquids by Gas Chromatography and Sulfur Selective Detection
• Effective Date: 01-Mar-2024
• Refers: ASTM D6300-24 - Standard Practice for Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products, Liquid Fuels, and Lubricants
• Effective Date: 01-Mar-2024
• Refers: ASTM D6299-23a - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• 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 D6300-23a - Standard Practice for Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products, Liquid Fuels, and Lubricants
• Effective Date: 01-Dec-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 D2892-23 - Standard Test Method for Distillation of Crude Petroleum (15-Theoretical Plate Column)
• Effective Date: 01-Nov-2023
• Refers: ASTM D4626-23 - Standard Practice for Calculation of Gas Chromatographic Response Factors
• Effective Date: 01-Oct-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 D2892-20 - Standard Test Method for Distillation of Crude Petroleum (15-Theoretical Plate Column)
• Effective Date: 01-Jun-2020
• Refers: 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-Dec-2019
• Refers: ASTM D6352-19 - Standard Test Method for Boiling Range Distribution of Petroleum Distillates in Boiling Range from 174 °C to 700 °C by Gas Chromatography
• Effective Date: 01-Dec-2019
• Refers: ASTM D6352-19e1 - Standard Test Method for Boiling Range Distribution of Petroleum Distillates in Boiling Range from 174 °C to 700 °C by Gas Chromatography
• Effective Date: 01-Dec-2019
• Refers: ASTM D6300-19a - Standard Practice for Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products and Lubricants
• Effective Date: 01-Dec-2019

Overview

ASTM D7807-20 is the standard test method for determining the boiling range distribution of hydrocarbon and sulfur components in petroleum distillates using gas chromatography and chemiluminescence detection. Developed by ASTM International, this method enables accurate analysis of the boiling range and sulfur distribution in light and medium petroleum distillates with final boiling points up to 538 °C (1000 °F). The method is valuable in refining operations, product specification testing, and quality control for petroleum products.

Gas chromatography replaces traditional distillation, offering precise and efficient measurement of both hydrocarbon and sulfur profiles. The integration of flame ionization detection (FID) and sulfur chemiluminescence detection (SCD) ensures comprehensive analysis of hydrocarbon and sulfur components, making the method suitable for industry compliance and process optimization.

Key Topics

• Boiling Range Determination: Simulates traditional distillation by using gas chromatography to elute hydrocarbon components in order of increasing boiling point.
• Sulfur Distribution Analysis: Employs chemiluminescence detection to quantify sulfur content and distribution, providing detailed insight into sulfur species across the boiling range.
• Applicability: Suitable for petroleum distillates with boiling points up to 538 °C and sulfur concentrations generally above 10 mg/kg.
• Instrument Requirements: Utilizes both FID and SCD detectors with open tubular capillary columns and precise temperature programming to achieve accurate separation and detection.
• Sample Limitations: Not applicable to samples with low molecular weight (e.g., gasoline, naphthas, crude oils) or those containing heterogeneous compounds such as alcohols, ethers, acids, or esters.

Applications

ASTM D7807-20 is widely used in:

• Petroleum Refining: Provides vital data for controlling and optimizing refining processes by monitoring the boiling range and sulfur content in feeds and products.
• Environmental Compliance: Supports measurement of sulfur content in accordance with environmental regulations, addressing concerns over emissions and product quality.
• Catalyst Protection: Assists in identifying sulfur compounds that may contribute to catalyst poisoning or corrosion of processing equipment.
• Product Specification Testing: Enables mutual agreement testing for product certification and quality assurance between parties.
• Process Development: Facilitates the evaluation of new refining methods and the efficiency of sulfur removal technologies.
• Replacement of Conventional Distillation: Offers a faster, more precise alternative to conventional boiling range determination methods, ensuring alignment with modern laboratory capabilities.

Related Standards

Professionals working with ASTM D7807-20 may also reference or use the following related ASTM standards for complementary analyses:

• ASTM D2887: Boiling Range Distribution of Petroleum Fractions by Gas Chromatography
• ASTM D86: Distillation of Petroleum Products at Atmospheric Pressure
• ASTM D1160: Distillation at Reduced Pressure
• ASTM D2622, D3120, D5504, D5623: Methods for Measuring Sulfur Content in Petroleum Products
• ASTM D2892: Distillation of Crude Petroleum
• ASTM D3710, D7096, D5307, D7169, D7500: Various methods for boiling range distributions and specialized petroleum product analysis

Practical Value

Adopting ASTM D7807-20 ensures consistent, reliable data for the boiling range and sulfur distribution in petroleum distillates. This empowers refineries and quality assurance laboratories to:

• Increase process efficiency with rapid, automated boiling range assessments.
• Enhance compliance with sulfur-related regulations.
• Minimize risks related to equipment degradation and catalyst poisoning.
• Deliver precise product quality data for customer and regulatory requirements.

By leveraging gas chromatography and advanced detection methods, ASTM D7807-20 sets a benchmark for analytical excellence in modern petroleum laboratories.

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: D7807 − 20
Standard Test Method for
Determination of Boiling Range Distribution of Hydrocarbon
and Sulfur Components of Petroleum Distillates by Gas
Chromatography and Chemiluminescence Detection
This standard is issued under the fixed designation D7807; 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* 1.5 The values stated in SI units are to be regarded as
standard. The values given in parentheses are for information
1.1 This test method covers the determination of the boiling
only.
range distribution of petroleum products. The test method is
1.6 This standard does not purport to address all of the
applicable to petroleum products and fractions having a final
safety concerns, if any, associated with its use. It is the
boiling point of 538 °C (1000 °F) or lower at atmospheric
responsibility of the user of this standard to establish appro-
pressure as measured by this test method. This test method is
priate safety, health, and environmental practices and deter-
limited to samples having a boiling range greater than 55 °C
mine the applicability of regulatory limitations prior to use.
(100 °F),andhavingavaporpressuresufficientlylowtopermit
1.7 This international standard was developed in accor-
sampling at ambient temperature.
dance with internationally recognized principles on standard-
1.1.1 The applicable sulfur concentration range will vary to
ization established in the Decision on Principles for the
some extent depending on the boiling point distribution of the
Development of International Standards, Guides and Recom-
sample and the instrumentation used; however, in most cases,
mendations issued by the World Trade Organization Technical
the test method is applicable to samples containing levels of
Barriers to Trade (TBT) Committee.
sulfur above 10 mg⁄kg.
1.2 This test method requires the use of both FID and SCD
2. Referenced Documents
for detection. The hydrocarbon simulated distillation data
2.1 ASTM Standards:
obtainedfromtheFIDsignalshouldbeperformedaccordingto
D86 Test Method for Distillation of Petroleum Products and
Test Method D2887 Procedure B.
Liquid Fuels at Atmospheric Pressure
1.3 The test method is not applicable for analysis of
D1160 Test Method for Distillation of Petroleum Products at
petroleum distillates containing low molecular weight compo-
Reduced Pressure
nents (for example, naphthas, reformates, gasolines, crude
D2622 Test Method for Sulfur in Petroleum Products by
oils). Materials containing heterogeneous components (for
Wavelength Dispersive X-ray Fluorescence Spectrometry
example, alcohols, ethers, acids, or esters) or residue are not to
D2887 Test Method for Boiling Range Distribution of Pe-
be analyzed by this test method. See Test Methods D3710,
troleum Fractions by Gas Chromatography
D7096, D5307, D7169,or D7500.
D2892 Test Method for Distillation of Crude Petroleum
(15-Theoretical Plate Column)
1.4 This test method does not purport to identify all sulfur
D3120 Test Method for Trace Quantities of Sulfur in Light
species in a sample. The detector response to sulfur is
Liquid Petroleum Hydrocarbons by Oxidative Microcou-
equimolar for all sulfur compounds within the scope (1.1)of
lometry
this test method. Thus, unidentified sulfur compounds are
D3710 Test Method for Boiling Range Distribution of Gaso-
determined with equal precision to that of identified sub-
line and Gasoline Fractions by Gas Chromatography
stances. Total sulfur content is determined from the total area
(Withdrawn 2014)
of the sulfur detector.
D4626 Practice for Calculation of Gas Chromatographic
1.4.1 This test method uses the principles of simulated
Response Factors
distillation methodology.
1 2
This test method is under the jurisdiction of ASTM Committee D02 on For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
Subcommittee D02.04.0H on Chromatographic Distribution Methods. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved May 1, 2020. Published June 2020. Originally the ASTM website.
approved in 2019. Last previous edition approved in 2019 as D7807 – 19. DOI: The last approved version of this historical standard is referenced on
10.1520/D7807-20. www.astm.org.
*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
D7807 − 20
D5307 Test Method for Determination of Boiling Range area count equal to 99.5 % of the total sample area under the
Distribution of Crude Petroleum by Gas Chromatography chromatogram is obtained.
(Withdrawn 2011)
3.2.5 initial boiling point (IBP), n—the temperature (corre-
D5504 TestMethodforDeterminationofSulfurCompounds
spondingtotheretentiontime)atwhichacumulativecorrected
in Natural Gas and Gaseous Fuels by Gas Chromatogra-
area equal to 0.5 % of the total sample area under the
phy and Chemiluminescence
chromatogram is obtained.
D5623 Test Method for Sulfur Compounds in Light Petro-
3.2.6 response factor (RF), n—the factor used in order to
leum Liquids by Gas Chromatography and Sulfur Selec-
calculate the mg/kg sulfur recovery of the sample.
tive Detection
D6299 Practice for Applying Statistical Quality Assurance
3.2.7 slice rate, n—the time interval used to integrate the
and Control Charting Techniques to Evaluate Analytical
continuous (analog) chromatographic detector response during
Measurement System Performance
an analysis. The slice rate is expressed in Hz (for example,
D6300 Practice for Determination of Precision and Bias
integrations or slices per second).
Data for Use in Test Methods for Petroleum Products,
3.2.8 slice time, n—the cumulative slice rate (analysis time)
Liquid Fuels, and Lubricants
associatedwitheachareaslicethroughoutthechromatographic
D6352 Test Method for Boiling Range Distribution of Pe-
analysis.Theslicerateisthetimeattheendofeachcontiguous
troleum Distillates in Boiling Range from 174 °C to
area slice.
700 °C by Gas Chromatography
D7096 Test Method for Determination of the Boiling Range 3.2.9 total sample area, n—the cumulative corrected area
Distribution of Gasoline by Wide-Bore Capillary Gas
from the initial point to the final area point.
Chromatography
3.3 Abbreviations—Acommon abbreviation of hydrocarbon
D7169 Test Method for Boiling Point Distribution of
compounds is to designate the number of carbon atoms in the
Samples with Residues Such as Crude Oils and Atmo-
compound. A prefix is used to indicate the carbon chain form,
spheric and Vacuum Residues by High Temperature Gas
while a subscripted suffix denotes the number of carbon atoms
Chromatography
(for example, normal decane n-C10, iso-tetradecane = i-C14).
D7500 Test Method for Determination of Boiling Range
Distribution of Distillates and Lubricating Base Oils—in
4. Summary of Test Method
Boiling Range from 100 °C to 735 °C by Gas Chroma-
tography 4.1 The boiling range distribution determination by distilla-
E178 Practice for Dealing With Outlying Observations
tion is simulated by the use of gas chromatography.Anonpolar
E355 Practice for Gas ChromatographyTerms and Relation- opentubular(capillary)gaschromatographiccolumnisusedto
ships
elute the hydrocarbon components of the sample in order of
E594 Practice for Testing Flame Ionization Detectors Used increasing boiling point. The column temperature is raised at a
in Gas or Supercritical Fluid Chromatography
reproduciblelinearrateandtheareaunderthechromatogramis
E1510 Practice for Installing Fused Silica Open Tubular
recorded throughout the analysis. Boiling points are assigned
Capillary Columns in Gas Chromatographs
to the time axis from a calibration curve obtained under the
same chromatographic conditions by analyzing a known mix-
3. Terminology
tureofhydrocarbonscoveringtheboilingrangeexpectedinthe
3.1 Definitions—This test method makes reference to many
sample. A quantitative standard is used to determine the SCD
common gas chromatographic procedures, terms, and relation-
detectorresponsefactor.Finally,thesamplesolutionisinjected
ships. Detailed definitions of these can be found in Practices
and with the use of the response factor, the amount of sample
E355, E594, and E1510.
recovered is calculated.After converting the retention times of
the sample slices to temperature, the boiling point distribution
3.2 Definitions of Terms Specific to This Standard:
can be calculated up to the recovered amount. From these data,
3.2.1 area slice, n—the area, resulting from the integration
the boiling range distribution can be obtained.
of the chromatographic detector signal, within a specified
retentiontimeinterval.Peakdetectionparametersarebypassed 4.1.1 By splitting the column effluent to FID and Sulfur
and the detector signal integral is recorded as area slices of Chemiluminescence Detector, simultaneous detection for hy-
consecutive, fixed duration time intervals. drocarbon (FID) and sulfur (SCD) components boiling range
distribution is obtained.The hydrocarbon simulated distillation
3.2.2 corrected area slice, n—an area slice corrected for
data should be calculated according to Test Method D2887.
baseline offset, by subtraction of the exactly corresponding
4.1.2 Alternatively, the FID may be used with the SCD
area slice in a previously recorded blank (non-sample) analy-
sis. detector superimposed over the FID and thus avoiding splitting
the sample through the column exit. This type of arrangement
3.2.3 cumulativecorrectedarea,n—theaccumulatedsumof
will lower the sensitivity of the detector in the sulfur mode.
correctedareaslicesfromthebeginningoftheanalysisthrough
a given retention time, ignoring any non-sample area (for
4.2 Asample aliquot is introduced into the chromatographic
example, solvent).
system.Samplevaporizationisprovidedbyseparateheatingof
3.2.4 final boiling point (FBP), n—the temperature (corre- the point of injection or in conjunction with column oven
spondingtotheretentiontime)atwhichacumulativecorrected heating.
D7807 − 20
4.3 The column oven temperature is raised at a reproducible determinethehydrocarbonboilingrangesofsuchsamples.The
linear rate to effect separation of the sample components in gas chromatographic determination of the sulfur boiling range
order of increasing boiling point. The elution of sample assists in process development, in treatment and control of
components is quantitatively determined using a flame ioniza- refining operations and is useful for assessing product quality.
tion detector and a sulfur chemiluminescence detector. The This determination produces detailed information about the
detector signal integral is recorded as area slices for consecu- sulfurdistributioninasamplethatcannotbeobtainedbyeither
tive retention time intervals during the analysis. total sulfur analysis or analysis of sulfur in discreet distillation
cuts.
4.4 Retention times of known normal paraffin hydrocarbons
5.2.1 The hydrocarbon boiling range distributions obtained
spanning the scope of this test method (C5- C44) are deter-
by Test Method D2887 are theoretically equivalent to those
mined and correlated to their theoretical boiling point tempera-
obtained by true boiling point (TBP) distillation (see Test
tures. The normalized cumulative corrected sample areas for
Method D2892). They are not equivalent to results from low
each consecutive recorded time interval are used to calculate
efficiency distillation such as those obtained with Test Method
the boiling range distribution. The boiling point temperature at
D86 or D1160.
each reported percent off increment is calculated from the
retention time calibration.
6. Apparatus
4.5 Sulfur Chemiluminescence Detection—As sulfur com-
6.1 Chromatograph—Any gas chromatograph, with hard-
pounds elute from the gas chromatographic column, they are
warenecessaryforinterfacingtoachemiluminescencedetector
processed in a heated combustion zone. The products are
and containing all features necessary for the intended applica-
collected and transferred to a sulfur chemiluminescence detec-
tion(s)canbeused.Thegaschromatographicsystemusedshall
tor(SCD).Thistechniqueprovidesasensitive,selective,linear
have the following performance characteristics:
response to volatile sulfur compounds and is used for the
6.2 ColumnTemperatureProgrammer—Thechromatograph
selective sulfur detection, while collecting hydrocarbon data
must be capable of linear programmed temperature operation
from the FID.
over a range sufficient to elute compounds up to a boiling
4.6 Alternative Detectors—This test method is written for
temperature of 538 °C (1000 °F) before reaching the upper end
the sulfur chemiluminescence detector but other sulfur specific
of the temperature program. The programming rate must be
detectors can be used provided they have sufficient linearity,
sufficiently reproducible to obtain retention time repeatability
sensitivity, and have equimolar response to all eluted sulfur
of 0.01 min (0.6 s, corresponding to approximately 0.5 °C) for
compounds, do not suffer from interferences, and satisfy
each component in the calibration mixture described in 7.7.
quality assurance criteria. Regulatory agencies may require
6.3 Detectors—ThistestmethodrequiresaFlameIonization
demonstration of equivalency of alternative detection systems
Detector (FID) and a Sulfur Chemiluminescence Detector
to the SCD.
(SCD).
6.3.1 FID—The FID shall meet or exceed the following
5. Significance and Use
specifications in accordance with Practice E594. Check the
5.1 The boiling range distribution of light and medium
detector according to the instrument manufacturer’s instruc-
petroleum distillate fractions provides an insight into the
tions.
composition of feed stocks and products related to petroleum
6.3.2 SCD—The sulfur chemiluminescence detector shall
refining processes. This gas chromatographic determination of
meet or exceed the following specifications: (1) greater than
boiling range can be used to replace conventional distillation 3
10 linearity, (2) less than 1 pg S/s sensitivity, (3) greater than
methods for control of refining operations. This test method 6
10 selectivity for sulfur compounds over hydrocarbons, (4) no
can be used for product specification testing with the mutual
quenching of sulfur compound response from co-eluting hy-
agreement of interested parties.
drocarbons when the same volume of sample is injected as for
5.2 This test method extends the scope of Test Method regular analysis, and (5) equimolar response (<610 %) on a
D2887 (538 °C) boiling range determination by gas chroma- sulfur basis.
tography to include sulfur boiling range distribution in the 6.3.2.1 For the purpose of boiling point calibration, the
petroleum distillate fractions. Knowledge of the amount of system must be capable of measuring sulfur compounds and
sulfur and its distribution in hydrocarbons is economically hydrocarbons simultaneously from a single column and
important in determining product value and in determining injection, for example, flame ionization detector with splitting
how best to process or refine intermediate products. Sulfur the column effluent prior to the sulfur chemiluminescence
compounds are known to affect numerous properties of petro- detector. Alternatively, a combined FID/SCD can also be used
leum and petrochemical products. The corrosion of metals and in order to obtain simultaneous sulfur and FID chromatogram.
poisoning of catalysts is of particular concern. In addition, the 6.3.2.2 Sulfurcompoundselutingfromthechromatographic
content of sulfur in various refined products may be subject to column are processed in a heated hydrogen-rich combustion
governmental regulations. Test Methods, such as, D2622, zone fitted to the end of the column. Products are transferred
D3120, D5504 and D5623, are available to determine total under reduced pressure to the reaction chamber of the chemi-
sulfur content or content of individual sulfur compounds in luminescence detector. An excess of ozone present in the
petroleum and petroleum products. Test Methods, such as, chamber reacts with the sulfur combustion product(s) to
D86, D1160, D2887, D3710, and D2892, are also available to liberate blue (480 nm) and ultraviolet light (260 nm).
D7807 − 20
TABLE 1 Typical Gas Chromatographic Conditions
6.3.3 DetectorSplitRequirements—Toensurethelowlevels
of sulfur are detected properly, the system must be capable to Instrument A gas chromatograph equipped with an on-column or
temperature programmable vaporizing injector (PTV)
detect the components in the system sulfur test mixture (see
8.9) with signal to noise (peak-to-peak) ratio of at least 100.
Column Capillary 10 m, 0.53 mm ID, 0.88 µm 100 % dimethyl-
Connections of the column to the detector shall be such that no polysiloxane stationary phase
temperature below the column temperature exists. Refer to
Flow Conditions 25 mL/min He carrier (constant flow)
Practice E1510 for proper installation and conditioning of the
Inlet Temperature: Programmed 100 °C to 350 °C at
capillary column.
25 °C ⁄min
6.4 Sample Inlet System—Any sample inlet system capable
Detector Split FID – SCD or SCD with FID Adapter
of meeting the performance specification in 8.7 may be used.
Programmed temperature vaporization (PTV) and program-
FID Temperature: 350 °C
mable cool on-column injection systems have been used 35 mL/min H2, 350 mL/min Air
successfully.
SCD Temperature: 950 °C
6.5 CarrierGasFlowControl—Thechromatographshallbe 10 mL/min O , 90 mL/min H
2 2
100 mL/min to 150 mL/min He or N make-up
equipped with carrier gas pressure or flow control capable of
maintaining constant carrier gas flow control through the
Oven 35 °C to 350 °C at 25 °C ⁄min
column throughout the column temperature program cycle.
Sample Injection 0.1 µL neat
6.6 Micro Syringe—A micro syringe with a 23 gauge or
smaller stainless steel needle is used for sample introduction.
Syringes of 0.1 µL to 10 µL capacity are commercially avail-
7.1.1 Additional purification is recommended by the use of
able. Automatic syringe injection is recommended.
molecular sieves or other suitable agents to remove water,
6.7 Column—This test method is limited to the use of
oxygen, and hydrocarbons. Available pressure shall be suffi-
non-polar wall coated open tubular (WCOT) columns.
cient to ensure a constant carrier gas flow rate.
6.7.1 Any column and conditions may be used that provide
7.2 Hydrogen—Hydrogen of at least 99.999 % (v/v) purity
separation of typical petroleum hydrocarbons in order of
(suitable for the flame ionization detector (FID). (Warning—
increasing boiling point and meet the column performance
Hydrogen is an extremely flammable gas under high pressure.)
requirements of 8.7.1 and 9.3.1.1.
6.7.2 Glass, fused silica, and stainless steel columns, with a
7.3 Air—High purity (for example, hydrocarbon-free) com-
0.53 mm diameter have been successfully used. Cross-linked
pressed air is used as the oxidant for the flame ionization
and bonded 100 % dimethyl-polysiloxane stationary phases
detector(FID).(Warning—Compressedairisagasunderhigh
with film thickness of 0.5 µm to 2.65 µm have been used. The
pressure and supports combustion.)
column length and liquid phase film thickness shall allow the
7.4 Oxygen—High purity (for example, hydrocarbon-free)
elution of at least C44 n-paraffin (BP = 545 °C).
compressed oxygen is used as the oxidant for the sulfur
6.8 Data Acquisition System—Use of an electronic integrat-
chemiluminescence detector (SCD). (Warning—Compressed
ing device or computer is mandatory for determining the
oxygen is a gas under high pressure and supports combustion.)
detector response and for boiling point calibration. The device
NOTE 2—Some SCD detectors allow the use of air instead of oxygen:
must have the following capabilities: (1) graphic presentation contacttheSCDmanufacturerforinformationontheuseofairasoxidant.
of the chromatogram, (2) digital display of chromatographic
7.5 Solvents—Unless otherwise indicated, it is intended that
peak areas, (3) measurement of area and time intervals, (4)
all solvents conform to the specifications of the committee on
calculation and use of response factors in accordance with
analytical Reagents of theAmerican Chemical Society where
Practice D4626, for example, external standardization, and (5)
such specifications are available.
the maximum area measured must be within the linear range of
7.5.1 Other grades may be used provided it is first ascer-
the measuring system used.
tained that the solvent is of sufficiently high purity to permit its
NOTE 1—Some gas chromatographs have an algorithm built into their
use without lessening the accuracy of the determination.
operating software that allows a mathematical model of the baseline
7.6 Cyclohexane (C H ), (99+ % pure) may be used as a
profile to be stored in memory. This profile is automatically subtracted
6 12
from the detector signal on subsequent sample runs to compensate for the
viscosity reducing solvent. It is miscible with asphaltic
column bleed. Some integration systems also store and automatically
hydrocarbons, however, it responds well to the FID. The
subtract a blank analysis from subsequent analytical determinations.
quality(hydrocarboncontent)shouldbedeterminedbythistest
method prior to use as a sample diluent. (Warning—
7. Reagents and Materials
Cyclohexane is flammable.)
7.1 Carrier Gas—Helium, of at least 99.999 % (v/v) purity
(Warning—Helium is a compressed gas under high pressure).
Any oxygen present is removed by a chemical resin filter
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
Standard-Grade Reference Materials, American Chemical Society, Washington,
(Warning—Follow the safety instructions from the filter
DC. For suggestions on the testing of reagents not listed by theAmerican Chemical
supplier.) The total amount of impurities should not exceed
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
10 mL⁄m . Helium or Nitrogen (at least 99.999 % (v/v)) can
U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
also be used as detector make-up gas. copeial Convention, Inc. (USPC), Rockville, MD.
D7807 − 20
7.7 Calibration Mixture—Anaccuratelyweighedmixtureof 8.4 The FID should be periodically inspected and, if
approximately equal mass quantities of n-hydrocarbons dis- necessary, remove any foreign deposits formed in the detector
solvedinasuitablesolvent.Themixtureshallcovertheboiling from combustion of silicone liquid phase or other materials.
range from n-C5 to n-C44, but does not need to include every Such deposits will change the response characteristics of the
carbon number, but at least sufficient number of points to
detector.
generate a reliable calibration curve and the C16 and C18.
8.5 SCD—Place in service in accordance with the manufac-
7.7.1 At least one compound in the mixture must have a
turer’s instructions. Optimization of the oxidant/fuel ratio is
boiling point lower than the IBPof the sample and at least one
critical for ensuring complete combustion of hydrocarbon
compound in the mixture must have a boiling point higher than
components in a sample. A flame or combustion zone that is
the FBP of the sample. Boiling points of n-paraffins are listed
too hydrogen rich will result in incomplete combustion. Matrix
in Table 2.
interference is occasionally observed when changing sample
7.7.2 If necessary, for the calibration mixture to have a
size. When matrix interference is indicated, samples may be
compound with a boiling point below the IBP of the sample,
analyzed by dilution or application of other mitigation efforts.
propane or butane can be added to the calibration mixture,
8.5.1 The typical flameless/combustion zone interface con-
non-quantitatively, by bubbling the gaseous compound into the
tains ceramic tubes in its construction. The performance of
calibration mixture in a septum sealed vial using a gas syringe.
these tubes is critical to performance of the SCD system.
7.7.3 Reference Material—Areference sample that has been
Compromised ceramic tubes are susceptible to matrix effects.
analyzed by laboratories participating in the test method
Compromised tubes may allow for reproducible duplicate
cooperative study. Consensus values for the boiling range
sample analysis but will fail QA procedures such as matrix
distribution of this sample are being determined.
dilution and spike analyses. Poorly functioning tubes can also
8. Preparation of Apparatus result in severe instrument drift, loss of equimolar response,
and general response instability. Compromised tubes must be
8.1 Gas Chromatograph Setup:
replaced to restore nominal instrument function.
8.2 Place the gas chromatograph and ancillary equipment
8.6 Column Conditioning—Anew column will require con-
into operation in accordance with the manufacturer’s instruc-
ditioning at the upper test method operating temperature to
tions. Recommended operating conditions are shown in Table
reduce or eliminate significant liquid phase bleed, resulting in
1.
a stable chromatographic baseline. Follow the guidelines
8.3 When attaching the column to the detector inlet, ensure
outlined in Practice E1510.
thattheendofthecolumnterminatesascloseaspossibletothe
FID jet. Follow the instructions in Practice E1510. 8.7 System Performance Specification:
A,B
TABLE 2 Boiling Points of Normal Paraffins
Carbon No. Boiling Point, °C Boiling Point, °F Carbon No. Boiling Point, °C Boiling Point, °F
1 −162 −259 23 380 716
2 −89 −127 24 391 736
3 −42 −44 25 402 755
4 0 31 26 412 774
5 36 97 27 422 791
6 69 156 28 431 808
7 98 209 29 440 825
8 126 258 30 449 840
9 151 303 31 458 856
10 174 345 32 466 870
11 196 385 33 474 885
12 216 421 34 481 898
13 235 456 35 489 912
14 254 488 36 496 925
15 271 519 37 503 937
16 287 548 38 509 948
17 302 576 39 516 961
18 316 601 40 522 972
19 330 626 41 528 982
20 344 651 42 534 993
21 356 674 43 540 1004
22 369 695 44 545 1013
A
API Project 44, October 31, 1972 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 D6352 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 D02.04.0H.
B
Used n-paraffin boiling points are traditionally 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.
D7807 − 20
8.7.1 Column Resolution—The column resolution, influ- 8.9 LinearityCheck—Alinearitycheckshouldbeperformed
enced by both the column physical parameters and operating after installation of the instrument or whenever maintenance is
conditions, affects the overall determination of boiling range performed. It is recommended to analyze known standards
distribution. Resolution is therefore specified to maintain with different levels of sulfur; or, dilute a known sulfur
equivalence between different systems (laboratories) employ- standardwithasulfur-freestandardwithasimilarboilingpoint
ing this test method. Resolution is determined using Eq 1 and distribution.
theC16andC18paraffinsfromthecalibrationmixtureanalysis
8.10 Recovery Check—To check the stability of the analysis
(see 7.7), and is illustrated in Fig. 1. Resolution (R) should be
system, a QC-sample analysis should be made at least every
at least three, using the identical conditions employed for
ten analyses. The total area for the sulfur components should
sample analyses:
not deviate more than 10 % from the value obtained in the
R 5 2~t 2 t ! ⁄ ~1.699 ~w 1 w !! (1) previous calibration run.
2 1 2 1
where:
9. Procedure
R = resolution,
9.1 Analysis Sequence Protocol—Define and use a predeter-
t = time(s) for the n-C16 peak maximum,
mined schedule of analysis events designed to achieve maxi-
t = time(s) for the n-C18 peak maximum,
mum reproducibility for these determinations. The schedule
w = peak width(s), at half height, of the n-C16 peak, and
will include cooling the column oven and injector to the initial
w = peak width(s), at half height, of the n-C18 peak.
starting temperature, equilibration time, sample injection and
8.7.2 Column Elution Characteristics—The recommended
system start, analysis, and final temperature hold time.
column liquid phase is a non-polar phase such as 100 %
9.1.1 After chromatographic conditions have been set to
dimethyl-polysiloxane.
meet performance requirements, program the column tempera-
ture upward to the maximum temperature to be used and hold
8.8 Sulfur Standard—A petroleum sample with a known
that temperature for the selected time. Following the analysis
total Sulfur content and a known boiling point distribution of
sequence protocol, cool the column to the initial starting
the sulfur (Warning—Sulfur compounds can be flammable
temperature.
and harmful or fatal when ingested or inhaled.).
9.1.2 Inject either the calibration mixture, solvent, or
8.8.1 Calculate the relative response factor for the Sulfur
sample into the chromatograph; or make no injection (baseline
Standard (see 8.8).
blank). At the time of injection, start the chromatograp
...

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: D7807 − 12 D7807 − 20
Standard Test Method for
Determination of Boiling Range Distribution of Hydrocarbon
and Sulfur Components of Petroleum Distillates by Gas
Chromatography and Chemiluminescence Detection
This standard is issued under the fixed designation D7807; 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. The test method is
applicable to petroleum products and fractions having a final boiling point of 538°C (1000°F)538 °C (1000 °F) or lower at
atmospheric pressure as measured by this test method. This test method is limited to samples having a boiling range greater than
55°C (100°F),55 °C (100 °F), and having a vapor pressure sufficiently low to permit sampling at ambient temperature.
1.1.1 The applicable sulfur concentration range will vary to some extent depending on the boiling point distribution of the
sample and the instrumentation used; however, in most cases, the test method is applicable to samples containing levels of sulfur
above 10 10 mg mg/kg.⁄kg.
1.2 This test method requires the use of both FID and SCD for detection. The hydrocarbon simulated distillation data obtained
from the FID signal should be performed according to Test Method D2887. Procedure B.
1.3 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 D3710, D7096, D5307, D7169,
or D7500.
1.4 This test method does not purport to identify all sulfur species in a sample. The detector response to sulfur is equimolar for
all sulfur compounds within the scope (1.1) of this test method. Thus, unidentified sulfur compounds are determined with equal
precision to that of identified substances. Total sulfur content is determined from the total area of the sulfur detector.
1.4.1 This test method uses the principles of simulated distillation methodology.
1.5 The values stated in SI units are to be regarded as standard. The values given in parentheses are for information only.
1.6 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 safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use.
1.7 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
D2622 Test Method for Sulfur in Petroleum Products by Wavelength Dispersive X-ray Fluorescence Spectrometry
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)
D3120 Test Method for Trace Quantities of Sulfur in Light Liquid Petroleum Hydrocarbons by Oxidative Microcoulometry
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. 15, 2012May 1, 2020. Published April 2013June 2020. Originally approved in 2019. Last previous edition approved in 2019 as D7807 – 19.
DOI: 10.1520/D7807-12.10.1520/D7807-20.
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
D7807 − 20
D3710 Test Method for Boiling Range Distribution of Gasoline and Gasoline Fractions by Gas Chromatography (Withdrawn
2014)
D4307 Practice for Preparation of Liquid Blends for Use as Analytical Standards
D4626 Practice for Calculation of Gas Chromatographic Response Factors
D5307 Test Method for Determination of Boiling Range Distribution of Crude Petroleum by Gas Chromatography (Withdrawn
2011)
D5504 Test Method for Determination of Sulfur Compounds in Natural Gas and Gaseous Fuels by Gas Chromatography and
Chemiluminescence
D5623 Test Method for Sulfur Compounds in Light Petroleum Liquids by Gas Chromatography and Sulfur Selective Detection
D6299 Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measure-
ment System Performance
D6300 Practice for Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products, Liquid Fuels, and
Lubricants
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
D7500 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
E178 Practice for Dealing With Outlying Observations
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. 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 % 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
equal to 0.5 % 0.5 % of the total sample area under the chromatogram is obtained.
3.2.6 response factor (RF), n—the factor used in order to calculate the mg/kg Sulfursulfur recovery of the sample.
3.2.7 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).
3.2.8 slice time, n—the cumulative slice rate (analysis time) associated with each area slice throughout the chromatographic
analysis. The slice rate is the time at the end of each contiguous area slice.
3.2.9 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-C10, iso-tetradecane = i-C14).
4. Summary of Test Method
4.1 The boiling range distribution determination by distillation is simulated by the use of gas chromatography. A nonpolar open
tubular (capillary) gas chromatographic column is used to elute the hydrocarbon components of the sample in order of increasing
The last approved version of this historical standard is referenced on www.astm.org.
D7807 − 20
boiling point. The column temperature is raised at a reproducible linear rate and the area under the chromatogram is recorded
throughout the analysis. Boiling points are assigned to the time axis from a calibration curve obtained under the same
chromatographic conditions by analyzing a known mixture of hydrocarbons covering the boiling range expected in the sample. A
quantitative standard is used to determine the SCD detector response factor. Finally, the sample solution is injected and with the
use of the response factor, the amount of sample recovered is calculated. After converting the retention times of the sample slices
to temperature, the boiling point distribution can be calculated up to the recovered amount. From these data, the boiling range
distribution can be obtained.
4.1.1 By splitting the column effluent to FID and Sulfur Chemiluminescence Detector, simultaneous detection for Hydrocar-
bonhydrocarbon (FID) and Sulfursulfur (SCD) components boiling range distribution is obtained. The Hydrocarbonhydrocarbon
simulated distillation data should be calculated according to Test Method D2887.
4.1.2 Alternatively, the FID may be used with the SCD detector superimposed over the FID and thus avoiding splitting the
sample through the column exit. This type of arrangement will lower the sensitivity of the detector in the sulfur mode.
4.2 A sample aliquot is 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 sample components in order
of increasing boiling point. The elution of sample components is quantitatively determined using a flame ionization detector and
a sulfur chemiluminescence 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 (C5- C44) are determined
and correlated to their theoretical 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.
4.5 Sulfur Chemiluminescence Detection—As sulfur compounds elute from the gas chromatographic column, they are
processed in a heated combustion zone. The products are collected and transferred to a sulfur chemiluminescence detector (SCD).
This technique provides a sensitive, selective, linear response to volatile sulfur compounds and is used for the selective sulfur
detection, while collecting hydrocarbon data from the FID.
4.6 Alternative Detectors—This test method is written for the sulfur chemiluminescence detector but other sulfur specific
detectors can be used provided they have sufficient linearity, sensitivity, and have equimolar response to all eluted sulfur
compounds, do not suffer from interferences, and satisfy quality assurance criteria. Regulatory agencies may require demonstration
of equivalency of alternative detection systems to the SCD.
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 processes. 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 Test Method D2887 (538°C)(538 °C) boiling range determination by gas
chromatography to include sulfur boiling range distribution in the petroleum distillate fractions. Knowledge of the amount of sulfur
and its distribution in hydrocarbons is economically important in determining product value and in determining how best to process
or refine intermediate products. Sulfur compounds are known to affect numerous properties of petroleum and petrochemical
products. The corrosion of metals and poisoning of catalysts is of particular concern. In addition, the content of sulfur in various
refined products may be subject to governmental regulations. Test Methods, such as, D2622, D3120, D5504 and D5623, are
available to determine total sulfur content or content of individual sulfur compounds in petroleum and petroleum products. Test
Methods, such as, D86, D1160, D2887, D3710, and D2892, are also available to determine the hydrocarbon boiling ranges of such
samples. The gas chromatographic determination of the sulfur boiling range assists in process development, in treatment and
control of refining operations and is useful for assessing product quality. This determination produces detailed information about
the sulfur distribution in a sample that cannot be obtained by either total sulfur analysis or analysis of sulfur in discreet distillation
cuts.
5.2.1 The hydrocarbon boiling range distributions obtained by Test Method D2887 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—Any gas chromatograph, with hardware necessary for interfacing to a chemiluminescence detector and
containing all features necessary for the intended application(s) can be used. The gas chromatographic system used shall have the
following performance characteristics:
D7807 − 20
6.2 Column Temperature Programmer—The chromatograph must be capable of linear programmed temperature operation over
a range sufficient to elute compounds up to a boiling temperature of 538°C (1000°F)538 °C (1000 °F) before reaching the upper
end of the temperature program. The programming rate must be sufficiently reproducible to obtain retention time repeatability of
0.01 min (0.6 s, 0.01 min (0.6 s, corresponding to approximately 0.5°C)0.5 °C) for each component in the calibration mixture
described in 7.7.
6.3 Detectors—This test method requires a Flame Ionization Detector (FID) and a Sulfur Chemiluminescence Detector (SCD).
6.3.1 FID—The FID shall meet or exceed the following specifications in accordance with Practice E594. Check the detector
according to the instrument manufacturer’s instructions.
6.3.2 SCD—The sulfur chemiluminescence detector shall meet or exceed the following specifications: (1) greater than 10
linearity, (2) less than 1 pg 1 pg S/s sensitivity, (3) greater than 10 selectivity for sulfur compounds over hydrocarbons, (4) no
quenching of sulfur compound response from co-eluting hydrocarbons when the same volume of sample is injected as for regular
analysis, and (5) equimolar response (<610 %) (<610 %) on a sulfur basis.
6.3.2.1 For the purpose of boiling point calibration, the system must be capable of measuring sulfur compounds and
hydrocarbons simultaneously from a single column and injection, for example, flame ionization detector with splitting the column
effluent prior to the sulfur chemiluminescence detector. Alternatively, a combined FID/SCD can also be used in order to obtain
simultaneous sulfur and FID chromatogram.
6.3.2.2 Sulfur compounds eluting from the chromatographic column are processed in a heated hydrogen rich hydrogen-rich
combustion zone fitted to the end of the column. Products are transferred under reduced pressure to the reaction chamber of the
chemiluminescence detector. An excess of ozone present in the chamber reacts with the sulfur combustion product(s) to liberate
blue (480 nm) (480 nm) and ultraviolet light (260 nm).(260 nm).
6.3.3 Detector Split Requirements—To ensure the low levels of sulfur are detected properly, the system must be capable to detect
the components in the system sulfur test mixture (see 8.9) with signal to noise (peak-to-peak) ratio of at least 100. Connections
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.
6.4 Sample Inlet System—Any sample inlet system capable of meeting the performance specification in 8.7 may be used.
Programmed temperature vaporization (PTV) and programmable cool on-column injection systems have been used successfully.
6.5 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.
6.6 Micro syringe—Syringe—A micro syringe with a 23 gauge or smaller stainless steel needle is used for sample introduction.
Syringes of 0.10.1 μL to 10 μL 10 μL capacity are commercially available. Automatic syringe injection is recommended.
6.7 Column—This test method is limited to the use of non-polar wall coated open tubular (WCOT) columns.
6.7.1 Any column and conditions may be used that provide separation of typical petroleum hydrocarbons in order of increasing
boiling point and meet the column performance requirements of 8.7.1 and 9.3.1.1.
6.7.2 Glass, fused silica, and stainless steel columns, with a 0.53 mm 0.53 mm diameter have been successfully used.
Cross-linked and bonded 100 % 100 % dimethyl-polysiloxane stationary phases with film thickness of 0.50.5 μm to 2.65 μm
2.65 μm have been used. The column length and liquid phase film thickness shall allow the elution of at least C44 n-paraffin (BP
= 545°C).545 °C).
6.8 Data Acquisition System—Use of an electronic integrating device or computer is mandatory for determining the detector
response and for boiling point calibration. The device must have the following capabilities: (1) graphic presentation of the
chromatogram, (2) digital display of chromatographic peak areas, (3) measurement of area and time intervals, (4) calculation and
use of response factors in accordance with Practice D4626, for example, external standardization, and (5) the maximum area
measured must be within the linear range of the measuring 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, of at least 99.999 % 99.999 % (v/v) purity (Warning—Helium is a compressed gas under high
pressure). Any oxygen present is removed by a chemical resin filter (Warning—Follow the safety instructions from the filter
supplier.) The total amount of impurities should not exceed 1010 mL ⁄m mL/m3. . Helium or Nitrogen (at least 99.999 % 99.999 %
(v/v)) can also be used as detector make-up gas.
7.1.1 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 at least 99.999 % 99.999 % (v/v) purity (suitable for the flame ionization detector (FID).
(Warning—Hydrogen is an extremely flammable gas under high pressure.)
D7807 − 20
TABLE 1 Typical Gas Chromatographic Conditions
Instrument A gas chromatograph equipped with an on-column or
temperature programmable vaporizing injector (PTV)
Column Capillary 10 m, 0.53 mm ID, 0.88 μm 100 % dimethyl-
polysiloxane stationary phase
Flow Conditions 25 mL/min He carrier (constant flow)
Inlet Temperature: Programmed 100°C to 350°C at 25°C/min
Inlet Temperature: Programmed 100 °C to 350 °C at
25 °C ⁄min
Detector Split FID – SCD or SCD with FID Adapter
FID Temperature: 350°C
FID Temperature: 350 °C
35 mL/min H2, 350 mL/min Air
SCD Temperature: 950°C
SCD Temperature: 950 °C
10 mL/min O , 90 mL/min H
2 2
100 – 150 mL/min He or N make-up
100 mL/min to 150 mL/min He or N make-up
Oven 35°C to 350°C at 25°C/min
Oven 35 °C to 350 °C at 25 °C ⁄min
Sample Injection 0.1 μL neat
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 Oxygen—High purity (for example, hydrocarbon-free) compressed oxygen is used as the oxidant for the sulfur
chemiluminescence detector (SCD). (Warning—compressedCompressed oxygen is a gas under high pressure and supports
combustion.)
NOTE 2—Some SCD detectors allow the use of air instead of oxygen,oxygen: contact the SCD manufacturer for information on the use of air as oxidant.
7.5 Solvents—unlessUnless 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.
7.5.1 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.
7.6 Cyclohexane (C H )—), (99+ % (99+ % pure) may be used as a viscosity reducing solvent. It is miscible with asphaltic
6 12
hydrocarbons, 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.)
7.7 Calibration Mixture—An accurately weighed mixture of approximately equal mass quantities of nhydrocarbonsn-
hydrocarbons dissolved in a suitable solvent. The mixture shall cover the boiling range from n-C5 to n-C44, but does not need to
include every carbon number, but at least sufficient number of points to generate a reliable calibration curve and the C16 and C18.
7.7.1 At least one compound in the mixture must have a boiling point lower than the IBP of the sample and at least one
compound in the mixture must have a boiling point higher than the FBP of the sample. Boiling points of n-paraffin’sn-paraffins
are listed in Table 2.
7.7.2 If necessary, for the calibration mixture to have a compound with a boiling point below the IBP of the sample, propane
or butane can be added to the calibration mixture, non-quantitatively, by bubbling the gaseous compound into the calibration
mixture in a septum sealed vial using a gas syringe.
7.7.3 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:
8.2 Place the gas chromatograph and ancillary equipment into operation in accordance with the manufacturer’s instructions.
Recommended operating conditions are shown in Table 1.
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.
D7807 − 20
A,B
TABLE 2 Boiling Points of Normal Paraffins
Carbon No. Boiling Point, °C Boiling Point, °F Carbon No. Boiling Point, °C Boiling Point, °F
1 −162 −259 23 380 716
2 −89 −127 24 391 736
3 −42 −44 25 402 755
4 0 31 26 412 774
5 36 97 27 422 791
6 69 156 28 431 808
7 98 209 29 440 825
8 126 258 30 449 840
9 151 303 31 458 856
10 174 345 32 466 870
11 196 385 33 474 885
12 216 421 34 481 898
13 235 456 35 489 912
14 254 488 36 496 925
15 271 519 37 503 937
16 287 548 38 509 948
17 302 576 39 516 961
18 316 601 40 522 972
19 330 626 41 528 982
20 344 651 42 534 993
21 356 674 43 540 1004
22 369 695 44 545 1013
A
API Project 44, October 31, 1972 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 D6352 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 D02.04.0H.
B
Used n-paraffin boiling points are traditionally 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,98.425 °C, which is correctly rounded to 98°C98 °C
in the table. However, converting 98.425°C98.425 °C gives 209.165°F,209.165 °F, which rounds to 209°F,209 °F, while converting 98°C98 °C gives 208.4°F,208.4 °F, which
rounds to 208°F.208 °F. Carbon numbers 2, 4, 7, 8, 9, 13, 14, 15, 16, 25, 27, and 32 are affected by rounding.
8.3 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.
8.4 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.
8.5 SCD—Place in service in accordance with the manufacturer’s instructions. Optimization of the oxidant/fuel ratio is critical
for ensuring complete combustion of hydrocarbon components in a sample. A flame or combustion zone that is too hydrogen rich
will result in incomplete combustion. Matrix interference is occasionally observed when changing sample size. When matrix
interference is indicated, samples may be analyzed by dilution or application of other mitigation efforts.
8.5.1 The typical flameless/combustion zone interface contains ceramic tubes in its construction. The performance of these tubes
is critical to performance of the SCD system. Compromised ceramic tubes are susceptible to matrix effects. Compromised tubes
may allow for reproducible duplicate sample analysis but will fail QA procedures such as matrix dilution and spike analyses.
Poorly functioning tubes can also result in severe instrument drift, loss of equimolar response, and general response instability.
Compromised tubes must be replaced to restore nominal instrument function.
8.6 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.
8.7 System Performance Specification:
8.7.1 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 C16 and C18 paraffins
from the calibration mixture analysis (see 7.7), and is illustrated in Fig. 1. Resolution (R) should be at least three, using the identical
conditions employed for sample analyses:
R 5 2~t 2 t ! ⁄ ~1.699 ~w 1 w !! (1)
2 1 2 1
where:
R = resolution,
t = time(s) fro the n-C16 peak maximum,
t = time(s) for the n-C16 peak maximum,
t = time(s) for the n-C18 peak maximum,
D7807 − 20
FIG. 1 Column Resolution Parameters
w = peak width(s), at half height, of the n-C16 peak, and
w = peak width(s), at half height, of the n-C18 peak.
8.7.2 Column Elution Characteristics—The recommended column liquid phase is a non-polar phase such as 100 % 100 %
dimethyl-polysiloxane.
8.8 Sulfur Compound Standards—99 + % purity (if available). Obtain pure standard material of all sulfur compounds of interest
(Warning—Sulfur compounds can be flammable and harmful or fatal when ingested or inhaled.). If purity is unknown or
questionable, analyze the individual standard material by any appropriate means and use the result to provide accurate standard
quantities.
8.9 System Sulfur Test Mixture—Gravimetrically prepare a solution of sulfur compounds at approximately 20 mg/kg sulfur in
ultra-low sulfur Diesel in accordance with Practice D4307. The test mixture should cover a broad boiling point range and should
be within the range of the hydrocarbon distribution.
8.9.1 For example, Benzothiophene, DiBenzothiophene, and 2,2'-dithiopyridine.
Name Formula Mol wt m/m%, S Boiling Point,
°C
Benzothiophene C H S 134.2 23.89 % 221
8 6
Dibenzothiophene C H S 184.26 17.40 % 332
12 8
2,2'-dithiopyridine C H N S 220.31 29.10 % 348
10 8 2 2
8.8 Sulfur Equimolarity—Standard—The SCD is an equimolar detector. Therefore, response factors for all sulfur components
should be within 10 %. Failure to satisfy this criterion indicates either system test mixture degradation or failure of the SCD
heatedA petroleum sample with a known total Sulfur content and a known boiling point distribution of the sulfur (Warning—
combustion zone or in other parts of the analysis system.Sulfur compounds can be flammable and harmful or fatal when ingested
or inhaled.).
8.8.1 Calculate the relative response factor for each sulfur compound in the System Sulfur test mixture the Sulfur Standard (see
8.98.8):).
8.8.2 Inject and analyze a suitable amount of the system sulfur test mixture standard (8.98.8). Relative response factors
shouldshall be calculated for each sulfur compound in the test mixture (relative to a referenced component) the Sulfur standard
in accordance with Practice D4626 or Eq 2.
C 3 A
n r
R 5 (2)
m
C 3 A
r n
where:
R = relative response factor for a given sulfur compound,
m
R = relative response factor for the Sulfur standard,
m
C = concentration of the sulfur compound as sulfur,
n
A = peak area of sulfur compound,
n
C = concentration of referenced sulfur standard as sulfur, and
r
A = peak area of the referenced sulfur standard.
r
8.10.2.1 The relative response factor (R ) for each sulfur compound should not deviate from the average response factor by
m
more than 10 %. Deviation of response by more than 10 % or severe peak asymmetry indicates a chromatography or detector
D7807 − 20
problem that must be corrected to ensure proper selectivity, sensitivity, linearity, and integrity of the system. If necessary, optimize
the system according to instructions from the manufacturer.
8.9 Linearity Check—A linearity check should be performed after installation of the instrument or whenever maintenance is
performed. It is recommended to analyze known standards with different levels of sulfur; or, dilute a known sulfur standard with
a sulfur-free standard with a similar boiling point distribution.
8.10 Recovery Check—To check the stability of the analysis system, a QC-sample analysis should be made at least every 10ten
analyses. The total area for the sulphursulfur components should not deviate more than 10 % 10 % from the value obtained in the
previous calibration run.
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 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
the corrected area slices of those time slices which precede the elution of any chromatographic unretained substance. If these corrected area slices
(representing the true baseline) deviate from zero, subtract the average of these corrected area slices from each corrected area slice in the analysis.
9.3 Retention Time versus Boiling Point Calibration—If this is the first time that an analysis is carried out, prepare the sequence
to include the retention time calibration standard, the Reference Gas Oil and a blank which is necessary to calculate the Boiling
Point Distribution of the Reference Gas Oil as well as for subsequent samples analysis. Calibration should be performed
weekyweekly when the instrument is in use, or whenever maintenance is performed and as dictated by the lab on-site precision
and or and/or Quality Control protocol. Inject an appropriate aliquot of the calibration mixture (see 7.7) into the chromatograph,
using the analysis sequence protocol. Obtain a normal (peak detection) data record in order to determine the peak retention times
and the peak areas for each component. Collect a time slice area record if a boiling range distribution report is desired. Fig. 32
illustrates a graphical plot of a calibration analysis.
9.3.1 Inspect the chromatogram of the calibration mixture for evidence of skewed (non-Gaussian shaped) peaks. Skewness is
often an indication of overloading the sample capacity of the column, which will result in displacement of the peak apex relative
to non-overloaded peaks. Distortion in retention time measurement and hence errors in boiling point temperature calibration will
be likely if column overloading occurs. The column liquid phase loading has a direct bearing on acceptable sample size. Reanalyze
the calibration mixture using a smaller sample size or a more dilute solution to avoid peak distortion.
9.3.1.1 Skewness Calculation—Calculate the ratio A/B on specified peaks in the calibration mixture as indicated by the
designations in Fig. 43. A is the width in seconds of the portion of the peak eluting prior to the time of the peak apex and measured
at 10 % 10 % of peak height (0.10-H), and B is the width in seconds of the portion of the peak eluting after the time of the peak
apex at 10 % 10 % of peak height (0.10-H). The skewness of all peaks shall be shall not be less than 0.5 nor more than 2.
9.3.2 Prepare a calibration table based upon the results of the analysis of the calibration mixture by recording the time of each
peak maximum and the boiling point temperature in degrees Celsius (or Fahrenheit) for every component in the mixture. Normal
paraffin boiling point temperatures (atmospheric equivalent temperatures) are listed in Table 2.
9.3.3 It is recommended to perform a calibration at the start and end of the sequence of analysis.
9.4 Sample Preparation—The amount of sample injected must not overload the column stationary phase capacity nor exceed
the detector linear range. A narrow boiling range sample will require a smaller amount injected than a wider boiling range sample.
Samples that are of low enough viscosity to be sampled with a syringe at ambient temperature may be injected neat. This type of
sample may also be diluted with an appropriate solvent (for example, cyclohexane) to control the amount of sample injected.
9.4.1 Samples that are too viscous or waxy to sample with a syringe may be diluted with an appropriate solvent.
D7807 − 20
FIG. 32 Chromatogram of DC to C dilutedDiluted in Cyclohexane
5 44
FIG. 43 Designation of Parameters for Calculation of Peak Skewness
9.5 Reference Gas Oil Analysis—Perform an analysis of the gas oil following the analysis sequence protocol. Collect the area
slice data and provide a boiling point distribution report as in Sections 10 and 11.
9.5.1 The results of this reference analysis must agree with the values given in Table 3 within the range specified by the test
method reproducibility (see Section 12). If it does not meet the criteria in Table 3, check that all hardware is operating properly
and all instrument settings are as recommended by the manufacturer. Rerun the retention boiling point calibration as described in
9.3.
9.5.2 Perform this reference gas oil confirmation test at least once per day or as often as required to establish confidence in
consistent compliance with 9.5.1.
9.6 Sample Analysis—Using the analysis sequence protocol inject a sample aliquot into the gas chromatograph. Collect a
contiguous time slice record of the entire analysis.
10. Calculations
10.1 Two signals are collected, one for the Hydrocarbons on the FID and one for the Sulfur on the SCD. For the
Hydrocarbonshydrocarbons on the FID the calculations should be performed according to Test Method D2887, for Sulfursulfur on
the SCD follow the calculations as described in 10.2 to 10.16.
10.2 Load the sample chromatograms slices into a table.
10.3 The number of slices required at the beginning of Datadata acquisition depends on chromatographic variables such as the
column flow, column film thickness, initial column temperature and column length. In addition, the detector signal level has to be
as low as possible at the initial temperature of the analysis. The detector signal level for both the sample signal and the blank at
the beginning of the run must be within 10 % 10 % for proper zeroing of the signals. Thus, the sampling frequency has to be
D7807 − 20
A
TABLE 3 Repeatability and Standard Deviation for the ASTM Reference Gas Oil in °C or °F Analyzed in the Sulfur Mode
m/m % BP (°C) BP (°C) BP (°C) BP (°C) BP (°C) Average ASTM Repeatability
Std. Dev.
IBP 179.4 181.3 180.6 182.1 180.3 180.7 4.2
5 251.0 252.4 252.4 252.3 252.3 252.1 1.8
10 272.1 273.3 273.5 273.5 273.5 273.2 1.5
15 288.6 290.9 290.4 290.2 289.9 290 3.1
20 301.8 304.0 302.7 302.6 302.5 302.7 2.8
25 312.1 314.9 313.6 313.4 313.0 313.4 3.7
30 320.3 322.6 321.3 321.1 321.0 321.3 3.1
35 328.7 330.8 329.9 329.6 329.3 329.7 2.9
40 335.6 337.2 336.5 336.1 336.0 336.3 2.5
45 342.2 344.0 343.5 342.9 342.7 343.1 2.9
50 349.8 351.2 350.8 350.4 350.2 350.5 2.2
55 356.5 358.0 357.7 357.1 357.0 357.3 2.6
60 364.6 365.9 365.8 365.1 365.1 365.3 2.5
65 372.9 374.0 374.0 373.2 373.2 373.5 2.3
70 381.8 382.5 382.6 381.9 381.9 382.1 1.7
75 391.2 391.9 392.1 391.5 391.4 391.6 1.6
80 400.9 401.6 402.0 401.3 401.2 401.4 1.7
85 411.9 412.6 413.1 412.3 412.4 412.5 1.8
90 425.3 426.0 426.6 425.6 425.7 425.8 2.1
95 444.4 445.3 446.2 444.8 444.7 445.1 2.8
FBP 494.6 498.1 501.2 497.4 495.2 497.3 9.0
m/m % BP (°F) BP (°F) BP (°F) BP (°F) BP (°F) Average ASTM Repeatability
Std. Dev
IBP 354.9 358.3 357.1 359.8 356.5 357.3 7.5
5 483.8 486.3 486.3 486.1 486.1 485.8 3.3
10 521.8 523.9 524.3 524.3 524.3 523.8 2.7
15 551.5 555.6 554.7 554.4 553.8 554.0 5.5
20 575.2 579.2 576.9 576.7 576.5 576.9 5.1
25 593.8 598.8 596.5 596.1 595.4 596.1 6.6
30 608.5 612.7 610.3 610.0 609.8 610.3 5.5
35 623.7 627.4 625.8 625.3 624.7 625.5 5.3
40 636.1 639.0 637.7 637.0 636.8 637.3 4.4
45 648.0 651.2 650.3 649.2 648.9 649.6 5.3
50 661.6 664.2 663.4 662.7 662.4 662.9 4.0
55 673.7 676.4 675.9 674.8 674.6 675.1 4.6
60 688.3 690.6 690.4 689.2 689.2 689.5 4.4
65 703.2 705.2 705.2 703.8 703.8 704.3 4.2
70 719.2 720.5 720.7 719.4 719.4 719.8 3.1
75 736.2 737.4 737.8 736.7 736.5 736.9 2.9
80 753.6 754.9 755.6 754.3 754.2 754.5 3.1
85 773.4 774.7 775.6 774.1 774.3 774.5 3.3
90 797.5 798.8 799.9 798.1 798.3 798.4 3.8
95 831.9 833.5 835.2 832.6 832.5 833.2 5.1
FBP 922.3 928.6 934.2 927.3 923.4 927.1 16.1
A
This data set is from one laboratory only.
adjusted so that at least a significant number of slices are acquired prior to the start of elution of sample or solvent. Adjust the
sampling frequency to obtain a minimum of 5 slices. These slices should not contain area counts due to either sample or solvent
elution.
10.4 Calculate the average slice offset at start of chromatogram as follows:
10.4.1 Verify the presence of large positive or negative slices by comparing the areas of each slice. These anomalies are
indication of an instrumental or chromatographic problem. These slices, if used, will cause erroneous results in the boiling point
distribution calculation.
10.4.2 Noisy signals and or and/or signals presenting spurious events may require the use of such techniques as Data Smoothing
or outliers determination as outlined in Practice E178. However, if good chromatographic principles are used, the occurrence of
these large negative or positive signals is rare. They will manifest themselves in the resulting chromatogram and are therefore
easily corrected.
10.5 Subtract the average slice offset from all the slices of the sample chromatogram. This will zero the chromatogram.
10.6 Load the blank run chromatogram slices into a table.
NOTE 4—For instruments that compensate the baseline directly at the detector producing an electronically corrected baseline, either process the sample
chromatogra
...