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: D8369 − 21

Standard Test Method for

Detailed Hydrocarbon Analysis by High Resolution Gas
Chromatography with Vacuum Ultraviolet Absorption
Spectroscopy (GC-VUV)1
This standard is issued under the fixed designation D8369; 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 1.2.3 Other compounds containing oxygen, sulfur, nitrogen,

1.1 This test method covers the use of gas chromatography
and vacuum ultraviolet absorption spectroscopy (GC-VUV) for
the determination of individual compounds and compound
classes by percent mass or percent volume with a final boiling
point as defined by Test Method D86 up to 225 °C.
1.1.1 Typical products encountered in petroleum refining or
biofuel operations, such as blend stocks; naphthas, reformates,
alkylates, FCC gasoline, liquefied petroleum gas (LPG), alco-
hols and ethers may be analyzed.
1.1.2 Spark-ignition engine fuels including those with com-
monly blended oxygenates may also be analyzed.
1.2 Individual compounds are spectrally verified and spe-
ciated. Compounds that are not spectrally verified and spe-
ciated are identified by carbon number, based on retention
index, and by class type, based on spectral response. The
resulting verified hydrocarbon analysis therefore identifies,
classifies, and reports 100 % of the spectral responses.
1.2.1 This test method may not be applicable to all concen-
trations of individual hydrocarbons; the user must evaluate the
spectral response of the hydrocarbon of interest, the amount
and proximity of co-eluting hydrocarbons, and detector satu-
ration. Quantitation of individual hydrocarbons with concen-
trations less than 0.1 % or greater than 30 % by mass may
require validation.
1.2.2 This test method can be used to determine methanol in
the range of 0.05 % to 3 % by mass, ethanol in the range of
0.05 % to 25 % by mass, butanols in the range of 0.5 % to
10 % by mass, methyl t-butyl ether (MTBE) in the range of
0.5 % to 22 % by mass, ethyl t-butyl ether (ETBE) in the range
of 0.5 % to 22 % by mass, and t-amyl methyl ether (TAME) in
the range of 0.5 % to 22 % by mass in spark-ignition engine
fuels.
NOTE 1—Applicable ranges of individual components and precision
will ultimately be defined by an interlaboratory study.
1
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 D02.04.0L on Gas Chromatography Methods.
Current edition approved April 1, 2021. Published May 2021. DOI: 10.1520/
D8369-21.
and so forth, may also be present, and may co-elute with the
hydrocarbons. If determination of other specific compounds is
required, supplementation of the spectral library may be
necessary.
1.3 Class-type composition – paraffins, iso-paraffins,
olefins, naphthenes, aromatics and oxygenates are reported.
The class composition totals are the sum of speciated indi-
vidual compounds and spectrally classed compounds.
1.3.1 The class types may optionally be sub classed by
carbon number.
1.3.2 Olefins may optionally be sub classed into mono-
olefins, non-conjugated diolefins, conjugated diolefins, and
cyclic olefins.
1.3.3 Aromatics may optionally be sub classed into mono-
aromatics, diaromatics, and naphtheno-aromatics (indans and
indenes).
NOTE 2—Interim precision for optional sub class reporting is not
determined.
1.4 Individual compounds may not be baseline-separated by
the procedure described in this method; that is, some com-
pounds will coelute. The coelutions are resolved at the detector
using VUV absorbance spectra and deconvolution algorithms.
1.5 This test method is intended as a type of detailed
hydrocarbon analysis (DHA). Incorporation of the GC-VUV
data report into commercial DHA software packages with
subsequent physical and chemical property calculations and
correlations is the responsibility of the DHA software vendor.
1.6 Temporary precision has been determined on a limited
subset of samples and compounds given in Table 6 and Table
7.
1.7 Units—The values stated in SI units are to be regarded
as standard. No other units of measurement are included in this
standard.
1.8 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 appro-
priate safety, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

1
 D8369 − 21
1.9 This international standard was developed in accor-
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ASTM Standards:2
D86 Test Method for Distillation of Petroleum Products and
Liquid Fuels at Atmospheric Pressure
D4057 Practice for Manual Sampling of Petroleum and
Petroleum Products
D4307 Practice for Preparation of Liquid Blends for Use as
Analytical Standards
D4814 Specification for Automotive Spark-Ignition Engine
Fuel
D5842 Practice for Sampling and Handling of Fuels for
Volatility Measurement
D6299 Practice for Applying Statistical Quality Assurance
and Control Charting Techniques to Evaluate Analytical
Measurement System Performance
D6300 Practice for Determination of Precision and Bias
Data for Use in Test Methods for Petroleum Products,
Liquid Fuels, and Lubricants
D6729 Test Method for Determination of Individual Com-
ponents in Spark Ignition Engine Fuels by 100 Metre
Capillary High Resolution Gas Chromatography
D6730 Test Method for Determination of Individual Com-
ponents in Spark Ignition Engine Fuels by 100-Metre
Capillary (with Precolumn) High-Resolution Gas Chro-
matography
D6792 Practice for Quality Management Systems in Petro-
leum Products, Liquid Fuels, and Lubricants Testing
Laboratories
D7372 Guide for Analysis and Interpretation of Proficiency
Test Program Results
D7900 Test Method for Determination of Light Hydrocar-
bons in Stabilized Crude Oils by Gas Chromatography
3. Terminology
3.1 Definitions:
3.1.1 integration filter, n—a mathematical operation per-
formed on an absorbance spectrum for the purpose of convert-
ing the spectrum to a single-valued response suitable for
representation in a two-dimensional chromatogram plot.
3.1.2 library reference spectrum, n—an absorbance spec-
trum representation of a molecular species stored in a library
database and used for identification of a compound/compound
class or deconvolution of multiple coeluting compounds.
3.1.3 response area, n—generally refers to a response
summed over a given time interval and has units of absorbance
units (AU).
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
2
3.1.3.1 Discussion—A time factor necessary to convert a
response area to a true mathematical area cancels out of all
critical calculations and is omitted.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 retention index, n—linear alkane retention indices are
assigned as multiples of 100 according to carbon number.
3.2.1.1 Discussion—A linear interpolation scheme between
n-alkanes along with retention index windows is sufficient to
narrow the search in the library database.
3.2.2 verified hydrocarbon analysis, n—the summed result
of spectrally verified, library matched components and com-
ponents identified by carbon number and class type.
3.3 Abbreviations:
3.3.1 AU—absorbance units
3.3.2 DHA—detailed hydrocarbon analysis
3.3.3 GC-VUV—gas chromatography with vacuum ultravio-
let absorption spectroscopy
3.3.4 RI—retention index
3.3.5 RRF—relative response factor
4. Summary of Test Method
4.1 A sample is introduced to a gas chromatographic (GC)
system. After volatilization, the effluent is introduced onto a
GC column for separation, and then detected by a vacuum
ultraviolet absorption spectroscopy detector.3 The separation is
accomplished using a 60 m, nonpolar phase capillary column
and a moderately fast temperature ramp (typical operating
parameters of this test method are given in Table 1). Coelutions
are resolved by the detector using vacuum ultraviolet absor-
bance spectra and deconvolution.
4.2 The result of the measurement is the determination of
the total response areas of the five hydrocarbon classes of
paraffins, isoparaffins, olefins, naphthenes, and aromatics, in
addition to individual species components. The percent mass
concentrations are calculated from the response areas using
class-based or compound-specific relative response factors, as
appropriate. The volume percent concentrations are calculated
from the mass concentrations by applying specific component
or class-based density values as appropriate.
5. Significance and Use
5.1 The determination of class group composition of hydro-
carbon streams and automotive spark-ignition fuels as well as
quantification of various individual species such as oxygenates
and aromatics is useful for evaluating quality and expected
performance.
3
The sole source of supply of the apparatus known to the committee at this time
is VUV-Analytics, Cedar Park, Texas. If you are aware of alternative suppliers,
please provide this information to ASTM International Headquarters. Your com-
ments will receive careful consideration at a meeting of the responsible technical
committee,1 which you may attend.
The vacuum ultraviolet absorption apparatus is covered by a patent. Interested
parties are invited to submit information regarding the identification of an
alternative(s) to this patented item to the ASTM International Headquarters. Your
comments will receive careful consideration at a meeting of the responsible
technical committee,1 which you may attend.
 D8369 − 21
TABLE 1 Typical Instrument Settings for GC-VUV Sample 7.6.1 The detector shall be able to interface with a gas
MeasurementA chromatographic system and measure an eluent with a scan
Standard Conditions frequency of at least 5 Hz with a baseline peak-to-peak noise
Capillary, 60 m × 0.25 mm ID ×
Column Dimensions width over a 10 s interval no greater than 0.002 AU when
0.25 µm film thickness
Column phaseB Nonpolar (for example, 100 % averaged over the following wavelength regions: 125 nm to
dimethyl polysiloxane)
Carrier GasC Helium
240 nm, 170 nm to 200 nm, 125 nm to 160 nm, and 0.001 AU
Injector temperature 250 °C when averaged over the 140 nm to 160 nm wavelength region.
Injection volumeD 1.0 µL 7.6.2 The detector shall be equipped with a shutter or
Split ratioD 300:1
Column flow (constant flow mode) 2.0 mL ⁄min
equivalent mechanism that allows the detector array to be
Oven initial temperature 5 °C blocked from the light source in order to perform a “dark”
Hold time 4 min measurement of electronic noise level.
Oven ramp 1 18 °C ⁄min
Oven temperature 1 50 °C
7.6.3 The detector shall be equipped with a flow cell capable
Hold time 14 min of being heated to at least 275 °C.
Oven ramp 2 5.5 °C ⁄min 7.6.4 The detector shall have an independently controlled
Final oven temperature 200 °C
Final Hold 0 min
makeup gas capability, capable of providing up to 5 mL ⁄min
Detector makeup gas pressure
as per manufacturer’s instructions
additional flow of nitrogen, helium, or argon to the flow cell.
(gauge)
Data scan rate 5.0 Hz 7.7 Data Processing System, capable of storing and pro-
Detector flow cell temperature 275 °C cessing absorbance scan data and corresponding time.
Transfer line temperature 275 °C
7.7.1 Data processing system shall include a database li-
brary3 of vacuum ultraviolet absorption reference spectra,
A
Alternate instrument settings are presented in Appendix X3.
B
Columns with low bleed phases such as MS grade have been successfully used
for this application (see 11.6). compound class information, carbon number, density, and
C
The typical flow rate is for helium carrier gas, other carrier gases may be utilized approximate retention index values. Data processing system
(see 8.2). shall also store relative response factors for each hydrocarbon
D
Other injection volumes and split ratios may be used to achieve the required
benzene response (see 13.2). class in addition to relative response factors for individually
reported compounds.
7.7.2 Data processing system shall be capable of imple-
6. Interferences menting equations and fit procedures that result in deconvolu-
tion of absorbance spectra that contain contributions from
6.1 Interferences with this test method, if any, have not been multiple species.
determined. 7.7.3 Data processing system shall be capable of binning
7. Apparatus and storing response contributions from each deconvolution
analysis and reporting a combined total response at the end of
7.1 Gas Chromatograph, equipped with automated oven the analysis.
temperature control and split/splitless inlet. 7.7.4 Data processing system shall be capable of imple-
7.1.1 Flow Controllers—The gas chromatograph must be menting equations to convert response areas to percent mass
equipped with mass flow controllers capable of maintaining and further convert percent mass to percent volume.
carrier gas flow constant to 61 % over the full operating
temperature range of the column. The inlet pressure of the 8. Reagents and Materials
carrier gas supplied to the gas chromatograph must be at least
485 kPa. This will ensure that the minimum pressure needed to 8.1 Purity of Reagents—Reagent grade chemicals shall be
compensate for the increase in column back-pressure as the used in all tests. Unless otherwise indicated, it is intended that
column temperature is maintained. all reagents shall conform to the specifications of the commit-
7.1.2 It is highly recommended that the gas chromatograph tee on Analytical Reagents of the American Chemical Society
is equipped with an autosampler. All statistical data were where such specifications are available.4 Other grades may be
obtained using a GC equipped with an autosampler. used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
7.2 Carrier Gas, for gas chromatograph: helium, nitrogen,
accuracy of the determination.
or hydrogen (see 8.2).
8.2 Nitrogen, helium, or hydrogen carrier gas for gas
7.3 Purge/Makeup Gas, for detector: helium, nitrogen, or
chromatograph, 99.999 % pure.
argon (see 8.3).
NOTE 3—Helium carrier gas was used to develop temporary precision
7.4 Oxygen, Water, Hydrocarbon Filters, to further purify statement.
GC carrier gas and detector purge/makeup gas.
7.5 Capillary Analytical Column, nonpolar (for example,
dimethyl polysiloxane) phase, dimensions 60 m length, 4
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
0.25 mm internal diameter, 0.25 µm film thickness. Standard-Grade Reference Materials, American Chemical Society, Washington,
DC. For suggestions on the testing of reagents not listed by the American Chemical
7.6 Vacuum Ultraviolet Absorption Spectroscopy Detector,
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
capable of measuring 125 nm to 240 nm absorbance spectra U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
with a wavelength resolution of 1 nm or better. copeial Convention, Inc. (USPC), Rockville, MD.

3
 D8369 − 21
8.3 Nitrogen, helium, or argon purge/makeup gas for stream standard. See Table 3. A typical chromatogram and an
vacuum ultraviolet absorption spectroscopy detector, 99.999 % example of a report are shown in Appendix X1.
pure.
9. Hazards
8.4 Methylene chloride, reagent grade, used as a solvent test
sample and GC rinse solvent. (Warning—Toxic material. May 9.1 Many of the compounds in automotive spark-ignition
be combustible at high temperatures.) engine fuel or other test samples used in this test method are
toxic, flammable, or both. Safety and sample-handling proce-
8.5 Retention time mixture consisting of iC4, C4, iC5, and
dures appropriate for working with such materials shall be in
C5 through C15 linear alkanes, approximately 1 % by mass
place before attempting to use this test method.
each, in suitable solvent such as methylene chloride.
8.5.1 The retention time mixture is used to determine a 10. Sampling
retention time marker list (see 12.1 and 12.2).
8.5.2 The retention time mixture is used to determine 10.1 Refer to Practices D4057 and D5842 for guidelines on
splitter linearity (see 13.3.2). obtaining volatile samples including automotive spark-ignition
engine fuel samples for analysis. Samples should be kept
8.6 A system validation mixture that complies with Practice refrigerated at approximately 4 °C until ready to be analyzed.
D4307, having the components and approximate concentra-
tions given in Table 2. The concentrations of the prepared 11. Preparation of Apparatus
system validation mixture should be close to those in Table 2
11.1 Ensure that all gas connections are properly made,
and shall otherwise be accurately known.
without leaks.
8.7 A quality control (QC) sample, similar in characteristics
11.2 Install oxygen, moisture, and hydrocarbon filters in gas
to samples that are to be routinely analyzed. Examples include
lines upstream of GC and detector. Maintain gas filters as
automotive spark-ignition fuel, naphtha, reformate, alkylate
instructed by manufacturer.
and FCC gasoline. See Section 18 Quality Control Monitoring.
11.3 Install the 60 m column in the GC inlet. Condition the
NOTE 4—Refer to Practices D6299 and D6792 for guidance on quality
assurance (QA) practices.
column according to the column manufacturer’s recommenda-
tions prior to installation in the detector.
8.8 A hydrocarbon stream standard used to set up the
spectrally verified peak table and define the report method (see 11.4 Perform maintenance on the GC as suggested by
12.8). The QC sample (8.7) can also be used as a hydrocarbon manufacturer, such as replacing septum and liner.
11.5 Configure the injector, carrier gas, and other GC
TABLE 2 System Validation Mixture
parameters according to Table 1.
Component Concentration (percent mass) 11.6 Inject the solvent test sample defined in 8.4 and run the
Cyclopentane 1.1 apparatus through a full oven ramp and cool-down cycle.
n-Pentane 1.1 Repeat.
Cyclohexane 2.1
2,3-Dimethylbutane 2.1
11.6.1 Assess the baseline on either a solvent test sample or
n-Hexane 2.1 a system validation mixture run (see 8.6). The average absor-
1-Hexene 1.5 bance value (125 nm to 240 nm) of at least a 0.1 min section of
Methylcyclohexane 4.0
4-Methyl-1-hexene 1.6
the baseline near the end of the oven ramp shall be no more
n-Heptane 3.5 than 60.0035 AU of the average value (125 nm to 240 nm) of
1,2-Dimethylcyclohexane 5.0 the initial 0.5 min to 1.0 min range.
Isooctane 5.0
n-Octane 5.0
1,2,4-Trimethylcyclohexane 4.0 12. Calibration and Standardization
n-Nonane 4.5
n-Decane 4.5
12.1 On installation of apparatus, after significant mainte-
n-Undecane 3.5 nance of apparatus, or after a significant method change,
n-Dodecane 3.5 establish a retention index file. Run the retention time mixture
Benzene 2.2
Toluene 2.2
(see 8.5) using the same flow conditions and oven ramp profile
trans-Decahydronaphthalene 4.0 as measured samples (see Table 1 for recommended run
n-Tetradecane 4.5 conditions). Record the retention times of iC4, C4, iC5, and C5
Ethylbenzene 4.5
o-Xylene 4.0
through C15 linear alkanes. These will serve as retention time
n-Propylbenzene 5.0 markers.
1,2,4-Trimethylbenzene 4.5 12.1.1 Significant method changes include changing the
1,2,3-Trimethylbenzene 5.0
1,2,4,5-Tetramethylbenzene 5.0
GC, column type, make-up gas pressure, or oven ramp profile.
Pentamethylbenzene 5.0 Significant maintenance of the apparatus includes replacing or
trimming the analytical column.
Total Paraffins 32.2
Total Isoparaffins 7.1 12.2 A list of retention times and retention indices for the
Total Olefins 3.1 branched and linear alkanes is used to estimate elution times of
Total Naphthenes 20.2
Total Aromatics 37.4 other compounds in the VUV library3 according to an interpo-
lation scheme. The retention index scheme sets the linear

4
 TABLE 3 Report Method Component Data
Component Class Carbon Retention Density at RRF Gasoline Petrol Alkylate Reformate Virgin Pyrolysis Naphtha Naphtha
Number Index 20 °C D4814 EN228 Naphtha Gas Coker FCC
g/mL
Propene Olefin 3 297.3 0.505 0.363
Propane Paraffin 3 300.0 0.501 0.872
Isobutane Isoparaffin 4 360.0 0.557 0.700 X X X X X
Methanol Oxygenate 1 370.4 0.792 1.299 X X
Isobutylene Olefin 4 386.9 0.595 0.387 X X
1-Butene Olefin 4 388.3 0.595 0.387 X X
1,3-Butadiene Olefin 4 393.3 0.621 0.340 X X
n-Butane Paraffin 4 400.0 0.579 0.800 X X X X X X X
Methyl mercaptan Sulfur 1 405.2 0.960 1.350 X
trans-2-Butene Olefin 4 407.5 0.604 0.387 X X X X X
cis-2-Butene Olefin 4 419.2 0.621 0.387 X X X X X
1,2-Butadiene Olefin 4 433.0 0.676 0.370 X X
Ethanol Oxygenate 2 445.6 0.789 1.013 X X
3-Methyl-1-butene Olefin 5 449.5 0.627 .0380 X X X X X
Isopentane Isoparaffin 5 470.4 0.620 0.740 X X X X X X X X
1,4-Pentadiene Olefin 5 474.4 0.661 0.370 X X
Dimethylacetylene Alkyne 4 477.0 0.678 0.400 X
1-Pentene Olefin 5 487.1 0.641 0.380 X X X X X
Isopropanol Oxygenate 3 489.1 0.786 0.863
Ethyl mercaptan Sulfur 2 490.0 0.862 0.735 X
2-Methyl-1-butene Olefin 5 495.1 0.650 0.380 X X X X X
n-Pentane Paraffin 5 500.0 0.626 0.730 X X X X X X X
2-Methyl-1,3-butadiene Olefin 5 503.7 0.681 0.340 X
trans-2-Pentene Olefin 5 506.9 0.648 0.380 X X X X X
cis-2-Pentene Olefin 5 513.4 0.656 0.380 X X X X

5
tert-Butanol Oxygenate 4 514.4 0.789 0.746
2-Methyl-2-butene Olefin 5 517.7 0.662 0.380 X X X X X
trans-1,3-Pentadiene Olefin 5 520.0 0.676 0.340 X X
Cyclopentadiene Olefin 5 528.0 0.650 0.465 X X
2,2-Dimethylbutane Isoparaffin 6 530.3 0.649 0.740 X X X X X X
D8369 − 21

cis-1,3-Pentadiene Olefin 5 530.8 0.682 0.340 X X

Isopropyl mercaptan Sulfur 3 540.5 0.820 0.600 X
Cyclopentene Olefin 5 546.3 0.772 0.465 X X X X X
n-Propanol Oxygenate 3 549.6 0.804 0.937
4-Methyl-1-pentene Olefin 6 551.5 0.667 0.400 X X X X X
3-Methyl-1-pentene Olefin 6 552.4 0.664 0.400 X X X X X
Cyclopentane Naphthene 5 556.6 0.745 0.828 X X X X X X X
2,3-Dimethylbutane Isoparaffin 6 559.9 0.662 0.740 X X X X X X X
Methyl tert-butyl ether Oxygenate 5 560.9 0.740 0.819 X
2,3-Dimethyl-1-butene Olefin 6 561.8 0.678 0.400 X X X X X
cis-4-Methyl-2-pentene Olefin 6 563.7 0.674 0.400 X X X X
2-Methylpentane Isoparaffin 6 565.6 0.653 0.740 X X X X X X X X
trans-4-Methyl-2-pentene Olefin 6 567.4 0.674 0.400 X X X X X
3-Methylpentane Isoparaffin 6 580.1 0.664 0.740 X X X X X X X X
1,5-Hexadiene Olefin 6 582.0 0.692 0.370 X
2-Methyl-1-pentene Olefin 6 586.2 0.685 0.400 X X X X X
1-Hexene Olefin 6 587.6 0.678 0.400 X X X X X
2-Butanol Oxygenate 4 590.9 0.808 0.905
trans-1,4-Hexadiene Olefin 6 592.0 0.710 0.370 X
n-Propyl mercaptan Sulfur 3 593.6 0.841 0.600 X
2-Ethyl-1-butene Olefin 6 599.4 0.689 0.400 X X X X
n-Hexane Paraffin 6 600.0 0.659 0.785 X X X X X X X
DIPE Oxygenate 6 601.9 0.725 0.837
trans-3-Hexene Olefin 6 602.2 0.682 0.400 X X X X X
cis-3-Hexene Olefin 6 602.9 0.685 0.400 X X X X X
 TABLE 3 Continued
Component Class Carbon Retention Density at RRF Gasoline Petrol Alkylate Reformate Virgin Pyrolysis Naphtha Naphtha
Number Index 20 °C D4814 EN228 Naphtha Gas Coker FCC
g/mL
trans-2-Hexene Olefin 6 604.2 0.683 0.400 X X X X X
2-Methyl-2-pentene Olefin 6 606.2 0.691 0.400 X X X X
cis-2-Hexene Olefin 6 611.8 0.692 0.400 X X X X X
Ethyl tert-butyl ether Oxygenate 6 617.2 0.736 0.766 X
trans-3-Methyl-2-pentene Olefin 6 617.2 0.702 0.400 X X X X X
Isobutanol Oxygenate 4 617.8 0.802 0.858
Methylcyclopentane Naphthene 6 620.8 0.749 0.805 X X X X X X X
2,4-Dimethylpentane Isoparaffin 7 626.1 0.673 0.760 X X X X X X X X
2,2,3-Trimethylbutane Isoparaffin 7 629.4 0.693 0.760 X X X X
1-Methyl-1,3-cyclopentadiene Olefin 6 632.1 0.706 0.465 X
1-Methylcyclopentene Olefin 6 642.4 0.780 0.500 X X X X
Benzene Aromatic 6 642.4 0.879 0.258 X X X X X X X
Thiophene Sulfur 4 646.6 1.051 0.260 X
sec-Butyl mercaptan Sulfur 4 647.0 0.830 0.650 X
3,3-Dimethylpentane Isoparaffin 7 648.4 0.693 0.760 X X X X X
n-Butanol Oxygenate 4 649.4 0.810 0.926
Cyclohexane Naphthene 6 651.0 0.779 0.805 X X X X X X
1,3-Cyclohexadiene Olefin 6 653.0 0.841 0.423 X
tert-Amyl alcohol Oxygenate 5 653.0 0.805 0.824
4-Methyl-1-hexene Olefin 7 658.4 0.705 0.455 X
cis/trans-4-Methyl-2-hexene Olefin 7 661.0 0.711 0.455 X X X X
2-Methylhexane Isoparaffin 7 663.0 0.679 0.760 X X X X X X X X
2,3-Dimethylpentane Isoparaffin 7 663.7 0.695 0.760 X X X X X X X X
1,1-Dimethylcyclopentane Naphthene 7 665.7 0.755 0.740 X X
tert-Amyl methyl ether Oxygenate 6 667.0 0.766 0.877 X

6
Cyclohexene Olefin 6 667.9 0.811 0.500 X X
3-Methylhexane Isoparaffin 7 671.6 0.687 0.760 X X X X X X X X
cis-3,4-Dimethyl-2-pentene Olefin 7 675.3 0.718 0.455 X X
cis-1,3-Dimethylcyclopentane Naphthene 7 677.6 0.745 0.740 X X X X X X
trans-1,3-Dimethylcyclopentane Naphthene 7 680.6 0.762 0.740 X X X X X X
D8369 − 21

3-Ethylpentane Isoparaffin 7 682.9 0.698 0.760 X X X X X X X

trans-1,2-Dimethylcyclopentane Naphthene 7 683.6 0.751 0.740 X X X X X
1-Heptene Olefin 7 686.5 0.697 0.455 X
Isooctane Isoparaffin 8 686.9 0.692 0.674 X X X X X
cis-3-Methyl-3-hexene Olefin 7 693.2 0.718 0.455 X X X X
n-Heptane Paraffin 7 700.0 0.684 0.780 X X X X X X
trans-2-Heptene Olefin 7 703.4 0.706 0.455 X X X X
cis-2-Heptene Olefin 7 709.3 0.712 0.455 X
cis-1,2-Dimethylcylopentane Naphthene 7 713.3 0.732 0.740 X X X
Methylcyclohexane Naphthene 7 713.7 0.769 0.740 X X X X X X X
1,1,3-Trimethylcyclopentane Naphthene 8 716.4 0.748 0.680 X X X
Ethylcyclopentane Naphthene 7 723.3 0.766 0.740 X X X X X X X
2,5-Dimethylhexane Isoparaffin 8 725.2 0.694 0.720 X X X X X X X
2.4-Dimethylhexane Isoparaffin 8 726.7 0.700 0.720 X X X X X X X
ctc-1,2,4-Trimethylcyclopentane Naphthene 8 731.1 0.743 0.680 X X X
ctc-1,2,3-Trimethylcyclopentane Naphthene 8 737.8 0.754 0.680 X X
2,3,4-Trimethylpentane Isoparaffin 8 740.8 0.719 0.720 X X X X
Toluene Aromatic 7 744.5 0.867 0.263 X X X X X X
2,3,3-Trimethylpentane Isoparaffin 8 744.9 0.726 0.720 X X X X
2-Methylthiophene Sulfur 5 745.8 1.014 0.270 X
2,3-Dimethylhexane Isoparaffin 8 751.6 0.712 0.720 X X X X X X X
1-Methylcyclohexene Olefin 7 754.6 0.811 0.500 X X
3-Methylthiophene Sulfur 5 754.6 1.027 0.270 X X
2-Methylheptane Isoparaffin 8 758.2 0.698 0.720 X X X X X X
3-Methylheptane Isoparaffin 8 766.5 0.706 0.720 X X X X X
 TABLE 3 Continued
Component Class Carbon Retention Density at RRF Gasoline Petrol Alkylate Reformate Virgin Pyrolysis Naphtha Naphtha
Number Index 20 °C D4814 EN228 Naphtha Gas Coker FCC
g/mL
1c,2t,3-Trimethylcyclopentane Naphthene 8 767.6 0.763 0.680 X X X
trans-1,4-Dimethylcyclohexane Naphthene 8 769.1 0.763 0.680 X X X X X
1,1-Dimethylcyclohexane Naphthene 8 775.5 0.781 0.680 X X
2,2,5-Trimethylhexane Isoparaffin 9 779.3 0.707 0.850 X X X X
3c-Ethylmethylcyclopentane Naphthene 8 780.2 0.767 0.680 X X X
3t-Ethylmethylcyclopentane Naphthene 8 782.7 0.767 0.680 X X X
1-Octene Olefin 8 784.5 0.765 0.451 X
2t-Ethylmethylcyclopentane Naphthene 8 784.3 0.769 0.680 X X
1-Ethyl-1-methylcyclopentane Naphthene 8 786.7 0.777 0.680 X
trans-1,2-Dimethylcyclohexane Naphthene 8 790.2 0.776 0.680 X X
n-Octane Paraffin 8 800.0 0.703 0.771 X X X X X X X
trans-2 Octene Olefin 8 803.2 0.720 0.451 X
cis-2-Octene Olefin 8 810.0 0.720 0.451 X
cis-1,2-Dimethylcyclohexane Naphthene 8 820.2 0.796 0.680 X X
1,1,4-Trimethylcyclohexane Naphthene 9 825.6 0.772 0.800 X X
Ethylcyclohexane Naphthene 8 831.1 0.784 0.680 X X
Ethylbenzene Aromatic 8 845.3 0.867 0.272 X X X X X X X
ctt-1,2,4-Trimethylcyclohexane Naphthene 9 848.2 0.780 0.800 X X
m-Xylene Aromatic 8 855.9 0.870 0.272 X X X X X X X
p -Xylene Aromatic 8 857.1 0.870 0.272 X X X X X X X
2-Methyloctane Isoparaffin 9 868.9 0.713 0.850 X X X X X X
ctc-1,2,3-Trimethylcyclohexane Naphthene 9 872.1 0.758 0.800 X X
Styrene Aromatic 8 873.7 0.909 0.270 X
3-Methyloctane Isoparaffin 9 875.3 0.721 0.850 X X X X X X
o-Xylene Aromatic 8 878.1 0.870 0.272 X X X X X X X

7
1-Nonene Olefin 9 890.5 0.768 0.490 X
n -Nonane Paraffin 9 900.0 0.718 0.780 X X X X X X X
trans-2-Nonene Olefin 9 903.9 0.734 0.490 X
Isopropylbenzene Aromatic 9 909.4 0.862 0.280 X X X X X
n-Propylbenzene Aromatic 9 942.0 0.862 0.280 X X X X X X X
D8369 − 21

1-Methyl-3-ethylbenzene Aromatic 9 950.4 0.865 0.280 X X X X X X X

1-Methyl-4-ethylbenzene Aromatic 9 952.2 0.861 0.280 X X X X X X X
1,3,5-Trimethylbenzene Aromatic 9 957.9 0.865 0.280 X X X X X X X
1-Methyl-2-ethylbenzene Aromatic 9 966.2 0.881 0.280 X X X X X X X
1,2,4-Trimethylbenzene Aromatic 9 980.4 0.876 0.280 X X X X X X X
1-Decene Olefin 10 990.3 0.741 0.474 X
Isobutylbenzene Aromatic 10 993.6 0.853 0.290 X X X X X
sec-Butylbenzene Aromatic 10 995.9 0.862 0.290 X X X X X
n-Decane Paraffin 10 1000.0 0.730 0.765 X X X X X X X
1,2,3-Trimethylbenzene Aromatic 9 1003.5 0.894 0.280 X X X X X X X
1-Methyl-3-isopropylbenzene Aromatic 10 1007.1 0.861 0.290 X X X X X X
1-Methyl-4-isopropylbenzene Aromatic 10 1010.1 0.857 0.290 X X X X X X
Dicyclopentadiene Olefin 10 1012.4 0.986 0.500 X
Indane Aromatic 9 1014.7 0.965 0.296 X X X X X X
Indene Aromatic 9 1021.4 0.996 0.265 X
1,3-Diethylbenzene Aromatic 10 1036.0. 0.860 0.290 X X X X X X
1-Methyl-3-n-propylbenzene Aromatic 10 1038.8 0.861 0.290 X X X X X X X
1-Methyl-4-n-propylbenzene Aromatic 10 1042.4 0.858 0.290 X X X X X X X
n-Butylbenzene Aromatic 10 1043.4 0.861 0.290 X X X X X X X
1,3-Dimethyl-5-ethylbenzene Aromatic 10 1045.9 0.88 0.290 X X X X X X X
1-Methyl-2-n-propylbenzene Aromatic 10 1053.6 0.874 0.290 X X X X X X X
1,4-Dimethyl-2-ethylbenzene Aromatic 10 1064.1 0.877 0.290 X X X X X X X
1,3-Dimethyl-4-ethylbenzene Aromatic 10 1065.6 0.859 0.290 X X X X X X X
1,2-Dimethyl-4-ethylbenzene Aromatic 10 1071.5 0.875 0.290 X X X X X X X
1-Undecene Olefin 11 1089.4 0.750 0.484 X
 TABLE 3 Continued
Component Class Carbon Retention Density at RRF Gasoline Petrol Alkylate Reformate Virgin Pyrolysis Naphtha Naphtha
Number Index 20 °C D4814 EN228 Naphtha Gas Coker FCC
g/mL
n-Undecane Paraffin 11 1100.0 0.740 0.755 X X X X X X
1,2,4,5-Tetramethylbenzene Aromatic 10 1100.8 0.888 0.290 X X X X X X X

8
1,2,3,5-Tetramethylbenzene Aromatic 10 1104.6 0.89 0.290 X X X X X X X
Naphthalene Aromatic 10 1160.6 1.025 0.198 X X X X X X X
n-Dodecane Paraffin 12 1200.0 0.753 0.745 X X X X X X
2-Methylnaphthalene Aromatic 11 1274.3 1.010 0.202 X X X X X X X
1-Methylnaphthalene Aromatic 11 1289.2 1.001 0.202 X X X X X X X
D8369 − 21

n-Tridecane Paraffin 13 1300.0 0.756 0.735 X X X X X X

 D8369 − 21
alkane retention indices to multiples of 100 according to
carbon number: butane RI = 400, pentane RI = 500, etc. Re-
tention indices of compounds eluting between n-alkanes are
linearly interpreted.
12.2.1 Once updated, the same retention time marker list is
used for all subsequent measurements until the next modifica-
tion or maintenance of the GC-VUV instrumentation.
12.3 The conversion from response areas to percent mass
uses compound specific response factors. The relative response
factors account for the differing areal response per unit mass
for the various compounds.
12.3.1 In cases where the identity of the specific compound
is not known, the conversion from response areas to percent
mass uses class-based and carbon number relative response
factors. The relative response factors account for the differing
areal response per unit mass for the various hydrocarbon
classes and carbon number (Table 3).
NOTE 5—A compound’s relative response factor is a function of the
type and number of chemical bonds. See Appendix X4.
12.4 For the purpose of this calculation, the response at a
given elution time refers to the absorbance averaged over the
125 nm to 240 nm wavelength region. The response area refers
to the sum of the response over all detector scans within a
given time region. A true area can be generated by multiplying
this quantity by the time interval between scans. However, this
step is unnecessary when the scan rate is kept constant
throughout a given measurement. For the purposes of this test
method, the response area is taken to be a sum having units of
absorbance units.
12.5 The response factors are relative to the response of
methane, which is taken to have a relative response factor of 1.
12.6 Relative response factors, densities, and retention in-
dices for individual components are given in Table 3. Hydro-
carbon class relative response factors are given in Table 4.
12.6.1 Individual components listed in Table 3 have been
spectrally verified, that is, the spectral response of the compo-
nent is known. The retention index provides further component
validation.
12.6.2 Other components of interest may be added to Table
3 provided that the spectral response and retention index are
known.
12.6.2.1 Conversely, components not of interest may be
deleted from Table 3.
12.7 The component’s retention index specified in Table 3
and the retention index window specified in Table 5 shall be
customized for different sample types. Larger retention index
windows accommodate high concentration components ensur-
TABLE 4 Relative Response Factors for Bulk Hydrocarbon
Classes
Hydrocarbon Class Relative Response Factor Range
Paraffin 0.697 – 1.00
Isoparaffin 0.713 – 0.850
Olefin 0.330 – 0.511
Naphthene 0.680 – 0.879
C9+ Aromatics 0.206 – 0.370
9
ing the entire peak is captured within the window and smaller
windows facilitate improved component identification and data
process speed.
12.7.1 A retention time window can be used in place of the
retention index window.
12.8 Only the individual components defined in the custom-
ized peak table are reported as spectrally verified. All other
components are reported based on class and carbon number.
Customized peak tables are referred to as report methods.
12.8.1 Examples of individual components of the report
method for different products are identified in Table 3 with an
“X”.
12.9 Each report method shall have a customized peak table
and an associated hydrocarbon stream standard (8.8).
12.10 Relative response factors may alternatively be refined
or determined as described in Appendix X2.
13. Pre-Measurement Validation
13.1 Before proceeding with measurements or after a sig-
nificant change or maintenance of the apparatus, the proce-
dures in Section 11 should have been completed, and a
retention index file generated or verified following the proce-
dure in 12.1 and 12.2.
13.2 Verify that the total response for benzene is 4.25 6
0.25 in the system validation mixture (see 8.6).
13.2.1 If the response is out of the specified range, adjust the
detector make-up gas pressure in 0.14 kPa increments and
reanalyze the system validation mixture, checking the benzene
response until it is in the specified range. Increasing the
detector make-up gas pressure will decrease the benzene
response. Do not adjust the make up gas pressure to less than
1.0 kPa or to more than 4.1 kPa.
13.2.2 If the detector make-up gas pressure has been
changed, reanalyze the retention index sample (see 12.1 and
12.2) and establish a new retention index file. Adjusting the
detector make-up gas pressure will change retention times.
Reanalyze the system validation mixture (see 8.6) and verify
the total response for benzene (see 13.2).
13.3 The system validation mixture (see 8.6) serves as a
verification of the analytical system.
13.3.1 System Accuracy—The system validation mixture
percent by mass results for total hydrocarbon group types
(paraffins, isoparaffins, olefins, naphthenes, and aromatics)
shall be within 610 % relative of the certified concentration
values.
13.3.2 Split Linearity—The ratio of tetradecane to pentane
shall be between 3.8 and 4.5.
13.3.2.1 If the split linearity results are unacceptable, verify
that the inlet seals, liner, and column position are designed to
minimize split inlet mass discrimination. A GC inlet liner
packed with deactivated glass wool is recommended.
13.3.3 The benzene, toluene, ethylbenzene, total xylenes,
and isooctane shall be within 60.2 % by mass of their known
values.
13.4 Analyze the hydrocarbon stream standard (8.8 and
12.9). Verify the spectral response against a library reference
 TABLE 5 Single Laboratory Percent Mass Repeatability Standard Deviations, Determined According to Practice D6300 Section 6.2.1
Analyte

Alkylate

Naphtha 1
Reformate

Gasoline 1
Gasoline 2
Gasoline 3
Gasoline 4
Gasoline 5
Gasoline 6
Fmax <4.85

VUVCS RFG
StdDev
StdDev
StdDev
StdDev
StdDev
StdDev
StdDev
StdDev
StdDev
StdDev
StdDev
StdDev

Average
Average
Average
Average
Average
Average
Average
Average FCC Naphtha 1
Average
Average
Average

Paraffin 8.65 0.21 5.64 0.16 10.2 0.26 14.0 0.09 9.36 0.13 9.33 0.26 5.14 0.10 3.47 0.03 21.6 0.1 9.68 0.10 0.763 0.03
Isoparaffin 42.2 0.25 68.57 0.20 22.1 0.31 38.4 0.20 32.5 0.28 28.0 0.23 40.2 0.33 35.4 0.36 30.1 0.5 26.2 0.19 96.3 0.35
Olefin 8.47 0.15 1.71 0.08 0.0843 0.02 5.18 0.08 10.6 0.14 6.33 0.11 6.86 0.09 17.1 0.25 0.178 0.020 0.261 0.03 0.0117 0.01
Naphthene 7.59 0.30 2.89 0.23 5.78 0.09 12.0 0.19 6.31 0.13 4.00 0.13 6.02 0.29 12.7 0.26 34.1 0.4 2.74 0.14 2.96 0.35
Aromatic 0.0008
21.6 0.25 21.2 0.1 61.9 0.6 22.1 0.15 34.3 0.49 42.5 0.52 28.3 0.22 31.3 0.40 14.0 0.0 61.1 0.23 0.00
Isobutane 0.342 0.022 0.395 0.033 0.150 0.009 1.071 0.094 0.127 0.012 0.206 0.016
n-Butane 1.202 0.072 3.626 0.152 2.376 0.136 0.930 0.035 2.005 0.121 3.259 0.207 1.171 0.063 0.135 0.009 0.831 0.044 0.275 0.017
trans-2-Butene 0.200 0.009 0.105 0.006 0.308 0.017
Ethanol 11.454 0.117 5.052 0.054 4.547 0.053
Isopentane 6.716 0.144 5.515 0.104 7.778 0.201 6.918 0.091 11.600 0.231 8.788 0.213 8.040
0.169 10.615 0.252 2.101 0.051 5.063 0.134
1-Pentene 0.217 0.006 0.149 0.003 0.512 0.010 0.140 0.003 0.188
0.006 0.611 0.017
2-Methyl-1-butene 0.529 0.013 0.292 0.004 1.064 0.018 0.124 0.006 0.417
0.009 1.210 0.029
n-Pentane 3.108 0.054 0.307 0.008 4.247 0.109 5.102 0.059 3.600 0.052 2.835 0.057 2.152
0.039 1.184 0.027 1.454 0.029 0.487 0.011
trans-2-Pentene 1.000 0.020 0.167 0.004 0.416 0.009 1.360 0.019 1.562 0.030 0.753
0.014 1.799 0.034
cis-2-Pentene 0.430 0.011 0.205 0.005 0.652 0.010 0.543 0.012 0.319
0.011 0.908 0.022
2-Methyl-2-butene 1.351 0.024 0.218 0.004 0.584 0.006 1.958 0.025 0.603 0.012 0.930
0.018 2.484 0.044
2,2-Dimethylbutane 0.427 0.006 0.117 0.004 0.254 0.006 1.996 0.011 1.467 0.016 0.158
0.003 0.267 0.005
Cyclopentene 0.123 0.212 0.153 0.222 0.006

10
Cyclopentane 0.299 0.007 0.475 0.012 0.736 0.011 0.398 0.009 0.212 0.006 0.172 0.004 0.197 0.007
2,3-Dimethylbutane 1.478 0.014 1.797 0.023 0.627 0.015 1.392 0.014 1.336 0.013 0.930 0.013 0.980 0.022 1.197 0.013 0.393 0.010 2.574 0.028
Methyl tert-butyl ether 5.686 0.052 1.451 0.024 1.153 0.016 13.444 0.099
2-Methylpentane 3.290 0.026 0.863 0.013 3.983 0.052 4.959 0.029 4.789 0.013 2.989 0.023 2.230 0.015 5.256 0.030 2.792 0.031 2.285 0.023 0.900 0.010
trans-4-Methyl-2-
D8369 − 21

0.166 0.004 0.154 0.002 0.119 0.004 0.108 0.004 0.266 0.005
pentene
3-Methylpentane 1.929 0.011 0.441 0.005 2.038 0.026 2.822 0.015 2.690 0.009 1.640 0.013 1.208 0.010 3.092 0.017 2.111 0.023 1.636 0.016 0.364 0.006
2-Methyl-1-pentene 0.202 0.012 0.191 0.006 0.107 0.005 0.127 0.009 0.396 0.004
n-Hexane 2.043 0.014 0.149 0.005 2.129 0.023 4.413 0.024 1.723 0.006 1.657 0.008 0.913 0.008 0.829 0.005 6.357 0.063 2.406 0.020
trans-3-Hexene 0.167 0.141 0.113 0.259 0.011
trans-2-Hexene 0.344 0.015 0.294 0.006 0.231 0.004 0.579 0.007
2-Methyl-2-pentene 0.380 0.020 0.197 0.004 0.355 0.023 0.251 0.004 0.291 0.016 0.632 0.029
cis-2-Hexene 0.149 0.002 0.134 0.004 0.107 0.005 0.302 0.005
trans-3-Methyl-2-
0.337 0.011 0.151 0.005 0.296 0.014 0.175 0.040 0.216 0.008 0.610 0.006
pentene
Methylcyclopentane 1.378 0.014 0.258 0.006 3.602 0.042 2.702 0.020 1.882 0.029 1.144 0.028 0.836 0.021 2.541 0.015 3.118 0.050 0.832 0.034
2,4-Dimethylpentane 1.119 0.011 4.514 0.022 0.589 0.008 0.853 0.006 0.329 0.005 0.375 0.006 1.340 0.008 0.429 0.026 0.341 0.010 0.529 0.012 9.055 0.030
1-Methylcyclopentene 0.169 0.010 0.194 0.022 0.174 0.012 0.330 0.033
Benzene 0.844 0.008 0.223 0.004 0.451 0.006 0.686 0.003 0.679 0.005 0.658 0.006 0.401 0.004 0.901 0.008 0.864 0.014 2.257 0.019
Cyclohexane 0.412 0.012 0.546 0.012 1.268 0.011 0.618 0.017 0.646 0.010 0.181 0.011 0.169 0.011 2.777 0.026
2-Methylhexane 1.721 0.046 2.516 0.538 1.929 0.056 1.727 0.036 1.284 0.024 1.400 0.030 0.926 0.121 2.768 0.022 2.812 0.029 3.428 0.033 0.845 0.497
2,3-Dimethylpentane 0.832 0.060 8.886 0.572 0.501 0.057 0.761 0.037 0.359 0.020 0.460 0.036 1.411 0.118 0.409 0.020 0.601 0.031 0.723 0.032 10.605 0.520
3-Methylhexane 1.543 0.011 1.398 0.011 1.672 0.005 1.644 0.007 1.317 0.010 1.484 0.006 0.854 0.005 2.132 0.013 2.885 0.014 3.621 0.017 0.364 0.011
cis-1,3-
0.341 0.011 0.109 0.006 0.370 0.003 0.584 0.006 0.259 0.010 0.132 0.008 0.245 0.005 0.947 0.008 1.129 0.007 0.149 0.008
Dimethylcyclopentane
trans-1,3-
0.281 0.006 0.266 0.005 0.504 0.008 0.222 0.008 0.115 0.005 0.202 0.004 0.816 0.021 1.021 0.012 0.157 0.009
Dimethylcyclopentane
3-Ethylpentane 0.131 0.049 0.139 0.060 0.150 0.029 0.129 0.036 0.147 0.038 0.133 0.031 0.230 0.042 0.370 0.041
 TABLE 5 Continued
trans-1,2-
0.265 0.037 0.178 0.029 0.720 0.028 0.233 0.031 0.178 0.035 0.494 0.026 1.609 0.038
Dimethylcyclopentane
Isooctane 7.641 0.055 16.975 0.056 5.274 0.022 1.553 0.022 3.5440.034 11.070 0.058 29.780 0.106
n-Heptane 1.228 0.013 1.024 0.006 0.932 0.006 1.965 0.009 1.275 0.021 1.1050.011 0.510 0.015 0.494 0.008 6.377 0.033 2.941 0.013
Methylcyclohexane 0.678 0.059 0.116 0.017 1.859 0.037 0.604 0.024 0.2500.023 0.402 0.031 1.118 0.018 6.625 0.059 0.160 0.014
Ethylcyclopentane 0.206 0.151 0.135 0.165 0.481 0.764 0.115 0.115
2,5-Dimethylhexane 1.219 0.033 1.245 0.070 0.872 0.062 0.306 0.036 0.388 0.040 0.918 0.049 0.259 0.032 0.331 0.011 0.365 0.010 1.726 0.090
2.4-Dimethylhexane 0.993 0.029 2.571 0.126 0.118 0.029 0.638 0.063 0.348 0.037 0.492 0.051 1.090 0.086 0.397 0.038 0.513 0.018 0.661 0.050 4.849 0.212
2,3,4-Trimethylpentane 2.677 0.046 5.576 0.026 2.468 0.029 0.567 0.024 1.114 0.017 2.161 0.059 7.428 0.039
Toluene 4.026 0.036 7.399 0.055 15.846 0.067 5.559 0.022 11.638 0.107 13.184 0.060 5.182 0.030 4.088 0.025 3.628 0.032 12.576 0.047
2,3,3-Trimethylpentane 2.689 0.054 2.425 0.098 2.457 0.084 1.553 0.110 5.240 0.039
2,3-Dimethylhexane 0.764 0.056 1.800 0.031 0.614 0.022 0.242 0.028 0.327 0.053 0.684 0.054 0.428 0.090 0.412 0.022 1.952 0.032
2-Methylheptane 0.631 0.081 0.490 0.065 0.358 0.033 0.668 0.031 0.527 0.061 0.378 0.043 0.408 0.054 1.147 0.063 2.773 0.033 1.552 0.038
3-Methylheptane 0.449 0.019 0.528 0.033 0.455 0.030 0.363 0.064 0.439 0.058 0.340 0.033 0.310 0.026 1.016 0.054 1.727 0.039 1.883 0.051
trans-1,4-
0.125 0.033 0.169 0.011 0.774 0.017
Dimethylcyclohexane
2,2,5-Trimethylhexane 1.433 0.027 2.319 0.023 0.500 0.015 0.168 0.027 0.189 0.040 1.349 0.046 2.921 0.025
n-Octane 0.399 0.137 0.421 0.005 0.344 0.004 0.889 0.017 0.587 0.041 0.371 0.025 4.533 0.076 1.467 0.009
Ethylbenzene 1.051 0.014 1.342 0.010 3.217 0.032 1.016 0.008 1.961 0.030 2.824 0.034 1.663 0.015 1.133 0.015 0.898 0.006 2.999 0.016
m-Xylene 2.478 0.027 3.926 0.028 7.973 0.174 3.182 0.025 5.331 0.093 6.324 0.085 2.882 0.023 3.817 0.045 2.253 0.011 7.716 0.053
p-Xylene 1.063 0.020 1.671 0.018 5.281 0.144 1.374 0.017 2.341 0.037 2.864 0.042 1.357 0.013 1.437 0.021 0.875 0.006 4.261 0.052
2-Methyloctane 0.183 0.080 0.130 0.065 0.118 0.038 0.571 0.034 0.814 0.055 0.506 0.042
3-Methyloctane 0.209 0.041 0.145 0.043 0.492 0.064 0.926 0.036 0.551 0.026
o-Xylene 1.411 0.017 2.005 0.017 4.883 0.056 1.674 0.014 2.750 0.046 3.693 0.053 2.097 0.019 1.771 0.022 1.062 0.005 4.016 0.020
n-Nonane 0.322 0.022 0.121 0.005 0.409 0.012 0.157 0.010 0.164 0.011 0.200 0.021 3.076 0.033 0.463 0.007
Isopropylbenzene 0.103 0.003 0.141 0.004 0.232 0.003 0.133 0.004 0.236 0.006 0.201 0.003 0.212 0.004
n-Propylbenzene 0.400 0.006 0.901 0.014 0.305 0.003 0.483 0.012 0.677 0.016 0.568 0.009 0.371 0.005 0.214 0.003 0.954 0.007
1-Methyl-3-
1.378 0.020 0.716 0.011 3.408 0.051 1.101 0.009 1.794 0.041 2.102 0.037 1.901 0.021 1.763 0.025 0.694 0.009 3.199 0.023
ethylbenzene

11
1-Methyl-4-
0.648 0.009 0.313 0.006 1.615 0.026 0.493 0.006 0.806 0.019 0.959 0.018 0.940 0.012 0.704 0.012 0.316 0.011 1.448 0.013
ethylbenzene
1,3,5-Trimethylbenzene 0.588 0.009 0.417 0.007 1.623 0.026 0.615 0.006 0.873 0.021 0.979 0.019 0.894 0.010 0.964 0.016 0.411 0.004 1.675 0.010
1-Methyl-2-
0.486 0.007 0.230 0.003 1.071 0.016 0.358 0.005 0.585 0.013 0.730 0.015 0.620 0.007 0.474 0.010 0.232 0.004 0.901 0.010
ethylbenzene
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1,2,4-Trimethylbenzene 2.129 0.031 1.450 0.022 5.625 0.081 1.986 0.017 2.745 0.065 3.579 0.070 2.943 0.031 2.998 0.043 0.990 0.009 4.757 0.028
n-Decane 0.199 0.009 0.227 0.010 0.144 0.013 0.196 0.012 1.107 0.014 0.117 0.006
1,2,3-Trimethylbenzene 0.468 0.009 0.281 0.005 1.152 0.020 0.399 0.006 0.509 0.012 0.760 0.015 0.604 0.008 0.608 0.011 0.184 0.004 0.843 0.006
Indane 0.255 0.004 0.506 0.008 0.147 0.003 0.145 0.004 0.277 0.006 0.449 0.006 0.392 0.005 0.112 0.003 0.468 0.003
1,3-Diethylbenzene 0.123 0.004 0.221 0.004 0.217 0.003 0.207 0.005 0.303 0.004
1-Methyl-3-n-
0.297 0.008 0.513 0.028 0.240 0.005 0.146 0.005 0.221 0.007 0.375 0.005 0.456 0.015 0.129 0.005 0.756 0.026
propylbenzene
1-Methyl-4-n-
0.163 0.007 0.347 0.008 0.133 0.003 0.120 0.003 0.240 0.006 0.261 0.005 0.436 0.006
propylbenzene
n-Butylbenzene 0.193 0.120 0.169 0.303 0.004
1,3-Dimethyl-5-
0.288 0.007 0.675 0.014 0.274 0.005174 0.170 0.007 0.260 0.010 0.388 0.007 0.587 0.011 0.138 0.003 0.785 0.007
ethylbenzene
1-Methyl-2-n-
0.206 0.111 0.133 0.258 0.004
propylbenzene
1,4-Dimethyl-2-
0.172 0.015 0.397 0.011 0.173 0.007203 0.109 0.013 0.177 0.007 0.220 0.011 0.308 0.025 0.382 0.011
ethylbenzene
1,3-Dimethyl-4-
0.178 0.013 0.415 0.008 0.161 0.006336 0.156 0.008 0.214 0.011 0.299 0.012 0.405 0.006
ethylbenzene
1,2-Dimethyl-4-
0.259 0.059 0.583 0.019 0.250 0.04833 0.132 0.038 0.250 0.037 0.354 0.031 0.424 0.053 0.560 0.029
ethylbenzene
1,2,4,5-
0.161 0.004 0.439 0.010 0.176 0.003275 0.103 0.005 0.192 0.006 0.226 0.005 0.389 0.012 0.430 0.004
Tetramethylbenzene
1,2,3,5-
0.219 0.006 0.594 0.017 0.245 0.00597 0.140 0.004 0.267 0.005 0.308 0.005 0.481 0.009 0.521 0.007
Tetramethylbenzene
 TABLE 5 Continued

Naphthalene 0.207 0.004 0.469 0.008 0.180 0.001677 0.132 0.003 0.280 0.004
0.526 0.008 0.672 0.019

12
2-Methylnaphthalene 0.168 0.004 0.295 0.006 0.179 0.00227 0.119 0.003
0.439 0.008 1.006 0.009
1-Methylnaphthalene 0.148 0.130 0.442 0.004
Total >> 87.018 0.292 86.850 0.228 95.930 0.128 89.287 0.177 93.579 0.200 93.880 0.186 87.675 0.319 80.244 0.296 81.224 0.412 88.727 0.210 84.428 0.279
D8369 − 21
 D8369 − 21
spectrum for individual components of interest. Define a
retention index window or alternatively a retention time
window that will capture these individual components of
interest in subsequent samples. A retention time window
should be only large enough to capture all expected concen-
trations of the component in subsequent samples.
13.5 Analyze the quality control sample defined in 8.7.
13.6 If the specifications in 13.3 or control limits in Section
5 are not met, verify the functionality of all GC-VUV
components, validity of retention time marker list, and validity/
quality of the QC or system validation mixture or both. Repeat
setup methodology in Sections 11, 12, and 13 as necessary to
ensure specifications in 13.3 and Section 5 are met before
proceeding.
13.7 It is recommended that the system validation mixture
or the QC sample, or both, be run with every subsequent batch
of 20 samples.
14. Procedure
14.1 Inject the sample into the GC injector port. Typical GC
method and detector conditions are given in Table 1.
14.2 The system shall record a dark scan immediately after
start.
14.3 The system shall record a reference scan immediately
after the dark scan.
14.3.1 The reference scan refers to an initial detector scan
used as a reference to convert subsequent detector scans to
absorbance scans, and is defined in Annex A1. It is not a library
reference spectrum.
14.4 The system shall record 125 nm to 240 nm absorbance
spectra and time of scan for each detector scan. Conversion of
recorded intensity data to absorbance is given in Annex A1.
14.5 At the end of the GC run, the data collection shall
automatically stop, and the recorded absorbance spectra pro-
cessed in order to obtain response areas for each of the
hydrocarbon classes and individual compounds being moni-
tored.
14.5.1 Calculate percent mass for each hydrocarbon class
and for individual compounds.
14.5.2 Calculate percent volume results from the percent
mass results and class/compound densities.
15. Calculation
NOTE 6—See pertinent information on modeling absorbance data in
Annex A2.
15.1 Divide the measured chromatogram into time slices of
a given width, ∆t. Define the following parameters:
15.1.1 A retention index (RI) window,
15.1.2 A chi-squared iteration threshold, expressed as a
percentage,
15.1.3 An R2 threshold,
15.1.4 A saturation threshold, and
15.1.5 An initial background time region (optional).
15.2 If an initial background time region is defined, calcu-
late a background spectrum from the average of the absorbance
scans over the background time region.
13
15.3 Analyze each time slice using the following algorithm:
15.3.1 Calculate the total absorbance from the sum of the
absorbance scans within the time slice.
15.3.1.1 If a background spectrum is defined, subtract the
background spectrum from each of the individual absorbance
spectra within the time slice. Sum the resulting background-
subtracted spectra to obtain the total absorbance spectrum for
the time slice.
15.3.1.2 If the absorbance value at a given wavelength
exceeds the saturation threshold for any of the absorbance
scans within the time slice, remove the data at that wavelength
value from the total absorbance and library reference spectra
used in subsequent fits for that time slice.
15.3.2 Calculate the average retention index of the time
slice using the average elution time of the time slice and the list
of retention time markers. A linear interpolation scheme is
sufficient.
15.3.3 Construct a list consisting of all compounds in the
VUV reference library within 6RI window of the average
retention index of the time slice.
15.3.4 Perform a tiered search on the total absorbance
spectrum, drawing from the constructed list of compounds:
15.3.4.1 Construct Eq A2.1 (see Annex A2) assuming a
single component contributes to the total absorbance. Select a
compound from the list and assign its library reference
spectrum to A1,ref in Eq A2.1. Fit the total absorbance to Eq
A2.1 using general linear least squares. Calculate a metric,
such as the chi-squared statistic:
1 N 1
x2 5 ( ~A 2 A i,calc ! 2 (1)
N i51 σ i2 i,meas
where:
N = the number of data points in an absorbance spec-
trum fit,
Ai,meas = the measured total absorbance at data point i,
Ai,calc = the calculated total absorbance at data point i, and
σi = the uncertainty of measured data point i, expressed
as a standard deviation.
If the uncertainty in the measured data have not been
estimated, the σi may be set to 1. Normalization by the number
of data points, N, is also optional.
15.3.4.2 Repeat the fit for each compound in the list and
retain the fit yielding the best chi-square value, along with the
best-fit compound’s fit value f1.
15.3.4.3 Construct Eq A2.1 assuming two compounds con-
tribute to the total absorbance spectrum. Populate A1,ref and
A2,ref in Eq A2.1 with library reference spectra for each
possible pair of compounds from the compound list. Fit the
total absorbance to Eq A2.1 for each pair. Retain the pair
resulting in the best chi-squared value along with their fit
values, f1 and f2. Compare the chi-squared value from the best
two-component fit to the chi-squared value from the best
one-component fit. If the percent improvement of the chi-
squared value for the best two-component fit over the best
one-component fit is greater than the chi-squared iteration
threshold, retain the two-component result. Otherwise, reject
the two-component result and retain the one-component result.
 D8369 − 21
15.3.4.4 Construct Eq A2.1 assuming three compounds
contribute to the total absorbance spectrum. Populate A1,ref,
A2,ref, and A3,ref with library reference spectra for each possible
triplet of compounds from the compound list. Fit the total
absorbance to Eq A2.1 for each triplet. Retain the triplet
resulting in the best chi-squared value along with the fit values,
f1, f2, and f3. Compare the chi-squared value from the best
three-component fit to the chi-squared value from the best
two-component fit. If the percentage improvement of the
chi-squared value for the best three-component fit over the best
two-component fit is greater than the chi-squared iteration
threshold, retain the best three-component result. Otherwise,
reject the three-component result and retain the best two-
component result, unless the best two-component result was
also rejected, in which case retain the best one-component
result.
15.3.5 The result of the tiered search procedure is a predic-
tion of the number of compounds that contribute to the total
absorbance spectrum, their likely identities, as well as the
best-fit values. “Integrate” the library reference spectra of the
best-fit compounds by averaging them over the 125 nm to
240 nm region, generating an integration factor for each
compound. Multiply the best-fit values, fi, by the correspond-
ing integration factors. These are the compounds’ contributions
to the response area of the time slice.
15.3.6 If the R2 value, determined from:
N
( ~A i,meas 2 A i,calc ! 2
2
R 512
i51
N (2)
2
i51
( ~A i,meas 2 Ā !
is less than the R2 threshold value, reject the analysis results
for the time slice (optional). Otherwise, add the compound
contributions to the total class response areas according to
their class, or to an individual compound’s response area if a
compound is one of the speciated compounds given in Table
3. If an individual compound in Table 3 also belongs to a
compound class in Table 4, add its response to the individual
compound response area and not to the class response area.
In Eq 2, Ā is the wavelength average of the measured total
absorbance spectrum.
15.3.7 Iterate the algorithm until all of the time slices have
been analyzed.
15.4 Implementation of an analysis criterion for determin-
ing whether to analyze a time slice and a background subtrac-
tion is permissible. If a background subtraction is used, a
criterion for automatically determining that a time region
should be used as a background spectrum may be defined.
15.4.1 Absorbance Check 1—Compare the change of a
response filter over a time slice. If the response filter changes
by more than the absorbance threshold, then analyze the time
slice. Otherwise, skip the time slice.
15.4.1.1 If a time slice is skipped, the background threshold
may be checked and if the response change over the time slice
is less than the background threshold, update the background
spectrum using the average absorbance spectrum over the time
slice.
15.4.2 Absorbance Check 2—If the maximum response of
the four filters consisting of average 125 nm to 240 nm
14
absorbance, average 170 nm to 200 nm absorbance, average
125 nm to 160 nm absorbance, and average 140 nm to 160 nm
absorbance exceeds the maximum response of the same four
filters applied to the current background spectrum by more than
three times the absorbance threshold, then analyze the time
slice (and do not update the background spectrum) regardless
of the outcome of Absorbance Check 1.
15.4.3 Other threshold criteria may be used, provided it is
first determined that use of alternate threshold criteria does not
lessen the accuracy or precision of the test method.
15.5 Due to the similarities of absorbance spectra of
compounds belonging to the same class, as well as the
similarities of relative response factors among compounds
belonging to the same class, it is not necessary to have an
explicit representation of all compounds in the VUV reference
library. The following substitutions for an uncharacterized
compound are permissible and will generally automatically be
made by the algorithm:
15.5.1 Library reference spectra of similar compound class
and similar carbon number.
15.5.2 Linear combinations of spectra of similar compound
class and similar carbon number.
15.6 If an R2 threshold is applied, record the amount of
response area rejected by implementation of the R2 threshold.
Compare the rejected amount to the total response area at the
end of the analysis. If more than 1.5 % of the response area was
rejected, the analysis should be flagged, and the measurement
data and GC-VUV instrumentation should be inspected.
15.7 Table 6 lists values for analysis parameters used in the
statistical study given in Section 17, and are suitable for use
with this test method.
15.8 The result of the measurement and analysis procedure
are total response areas for each of the hydrocarbon classes and
each individually speciated compound. For a given class or
specific compound, a, calculate the percent mass from:
A a 3 RRF a
M a 5 100 3 n (3)
( A 3 RRF
i51
i i
where:
Ma = percent mass for analyte or analyte class a,
Aa = total response area for analyte or analyte class a, and
RRFa = relative response factor for analyte or analyte class
a.
The sum runs over all hydrocarbon classes and speciated
compounds.
15.8.1 Calculate the total aromatics percent mass by adding
the percent mass for the individual monoaromatics and diaro-
matics.
15.9 If desired, calculate total saturate content by summing
the percent mass values of the hydrocarbon classes of paraffins,
isoparaffins, and naphthenes.
15.10 The percent mass result for analyte or analyte class
may be converted to percent volume using:
 D8369 − 21
TABLE 6 Parameters Used in Analysis of GC-VUV Scan Data
Parameter Value
Time slice width 0.01 min
RI window ±25
Initial background region 2.8 min to 3.0 min
Saturation threshold 1.2 AU
R2 threshold 0.4
Absorbance threshold 0.0005 AU
Background threshold 0.00025 AU
Background Scalar 1.5
Response filter to apply Absorbance Check 1 Average 140 nm to 160 nm absorbance
Response filter to apply background check Average 140 nm to 160 nm absorbance
Response filter(s) to apply Absorbance Check 2 Average 125 nm to 240 nm absorbance
Average 170 nm to 200 nm absorbance
Average 125 nm to 160 nm absorbance
Average 140 nm to 160 nm absorbance
Chi-square iteration threshold 60 %

Ma 17. Precision and Bias

ρa
V a 5 100 3 N
(S D
Mi
i51 ρi
where:
Ma = percent mass for analyte or analyte class a,
Mi = percent mass for analyte or analyte class i,
Va = percent volume for analyte or analyte class a,
ρa = liquid density for analyte or average liquid density for
analyte class a, and
ρi = liquid density for analyte or average liquid density for
analyte class i.
The liquid density values may be obtained from various
literature or ASTM publications. For example, liquid densities
for many relevant compounds are given in Test Method D6730
and in ASTM publication DS4A, Physical Constants of Hy-
drocarbons C1 to C10.5 Average liquid density values may be
used for densities of bulk classes or for classes at various
carbon numbers. Recommended densities for use with this test
method are given in Table 3.
15.10.1 Eq 4 shall be applied to percent mass values.
Calculate total aromatic percent volume by summing the
percent volume values of the aromatics and diaromatics.
15.10.2 Calculate total saturate percent volume by summing
the percent volume values of the hydrocarbon classes of
paraffins, isoparaffins, and naphthenes.
16. Report
16.1 The verified hydrocarbon analysis report shall distin-
guish between spectrally verified components and components
that are identified by class and carbon number.
16.2 Report the class totals percent mass and percent
volume to the nearest 0.01 % and the percent mass and percent
volume for individual compounds to the nearest 0.001 %.
16.3 Reference this test method.
17.1 The repeatability and reproducibility will ultimately be
(4)
determined by an interlaboratory study6 in accordance with
ASTM methodology. This section reports temporary, single-
laboratory repeatability standard deviations for the quantities
listed in Table 5.
17.1.1 Repeatability tests were carried out by a single
laboratory on eleven samples – six gasolines, FCC naphtha,
virgin naphtha, reformate, and alkylate. In order to mitigate
effects of sample change during repeated measurement, each
sample was split into fourteen vials. Each vial was measured
one time, for a total of 14 measurements per sample using the
standard conditions in Table 1. A detailed speciation and
hydrocarbon class type totals were determined during each
measurement. Table 5 shows the percent mass values of the
various parameters for the eleven samples for component
greater than 0.1 % by mass. The standard deviation was
calculated for all analytes that were present in a minimum of
three samples in accordance with section 6.2.1 of Practice
D6300, and the results are given in Table 5.
17.1.2 Repeatability tests were carried out by a single
laboratory on seven blends of oxygenates in gasoline. The
blends were optimized for eight common oxygenates at a low,
medium and high concentration. In order to mitigate effects of
sample change during repeated measurement, each sample was
split into twelve vials. Each vial was measured one time, for a
total of 12 measurements per sample using the standard
conditions in Table 1. A detailed speciation and hydrocarbon
class type totals were determined during each measurement.
Table 7 shows the percent volume values of the various
oxygenates for the seven samples. The repeatability standard
deviation was calculated for in accordance with section 6.2.1 of
Practice D6300, and the results are given in Table 7.
18. Quality Control Monitoring
18.1 Confirm the test method performance procedure by
regular analysis of quality control (QC) sample(s) (see Practice
D6299).

6
An interlaboratory study of this test method is being conducted and a complete
5
Available from ASTM International, West Conshohocken, PA, www.astm.org. precision statement is expected to be available on or before 2025.

15
 D8369 − 21
TABLE 7 Single Laboratory Oxygenates Percent Volume Repeatability Standard Deviations, Determined According to Practice D6300
Section 6.2.1
Repeatability Repeatability
Sample Analyte Average Vol % Sample Analyte Average Vol%
StdDev StdDev
Blend E Methanol 0.078 0.006 Blend E 1-Butanol 0.606 0.016
Blend F Methanol 1.673 0.015 Blend F 1-Butanol 8.00 0.087
Blend A Methanol 3.42 0.037 Blend A 1-Butanol 15.41 0.181
Blend A Ethanol 0.036 0.005 Blend A MTBE 0.599 0.006
Blend G Ethanol 14.57 0.162 Blend F MTBE 11.89 0.052
Blend B Ethanol 30.0 0.410 Blend C MTBE 24.10 0.145
Blend E tert-Butanol 0.537 0.006 Blend A TAME 0.566 0.011
Blend G tert-Butanol 1.858 0.018 Blend G TAME 12.70 0.041
Blend A tert-Butanol 2.97 0.033 Blend E TAME 24.21 0.099
Blend E 2-Butanol 0.550 0.004 Blend A ETBE 0.515 0.015
Blend G 2-Butanol 1.648 0.017 Blend D ETBE 24.30 0.037
Blend A 2-Butanol 3.26 0.037 Blend F ETBE 12.21 0.050

18.2 Record QC sample test results and confirm the statis-
tical control status (see Practice D6299) for the execution of
the complete test method using control charts (see Practice
D6299). Investigate any out-of-control result for root cause(s).
The outcome from this investigation may, but not necessarily,
result in instrument re-calibration.
18.3 The frequency of QC testing is dependent on the
criticality of the property being measured, the demonstrated
stability of the testing process, and business requirements.
Generally, a QC sample should be analyzed each testing day
with routine samples. The QC frequency should be increased if
a large number of samples are routinely analyzed. However,
when it is demonstrated that the testing is under statistical
control, the QC testing frequency may be reduced. The QC
sample testing precision should be periodically checked against
the ASTM International published method precision for con-
sistency (see Practice D6792).
18.4 The QC sample material (see Practice D6299) that is
regularly tested should be representative of the samples rou-
tinely analyzed. An ample supply of QC sample material
should be available for the intended period of use, and must be
homogenous and stable under the anticipated storage condi-
tions.
18.5 Participation in appropriate PT programs (if available)
is recommended for monitoring performance relative to indus-
try (see Guide D7372).
18.6 See Practice D6299, Practice D6792, and Guide D7372
for further guidance.
19. Keywords
19.1 alkylate; detailed hydrocarbon analysis; FCC naphtha;
gas chromatography; gasoline; naphtha; oxygenate; petrol;
pyrolysis gas; reformate; spark-ignition automotive fuel;
vacuum ultraviolet absorption spectroscopy; verified hydrocar-
bon analysis

ANNEXES

(Mandatory Information)

A1. GENERATING ABSORBANCE SPECTRA FROM INTENSITY SCAN DATA

A1.1 The following converts recorded scan intensity data to A1.1.2 After collecting dark and reference scans, the detec-
VUV absorbance spectra, assuming the availability of a previ- tor continues to collect intensity scans, I(λ), at regular intervals.
ously recorded dark intensity scan, Id(λ), and reference inten- The detector array typically has settings for scan time, in ms,
sity scan, Ir(λ). and number of averages per scan. The total time per scan is the
scan time multiplied by the number of averages. For example,
A1.1.1 The dark scan is collected at the beginning of the a scan time of 11 ms with 20 averages results in a scan rate of
chromatogram with the lamp shutter closed. The dark scan is about 4.5 scans ⁄s.
subtracted from all subsequent intensity scans. The reference
scan is collected at the beginning of the chromatogram with the A1.1.3 The absorbance is given by:
shutter open, but with only carrier/makeup gas flowing through
the flow cell. S ~ !D
A ~ λ ! 5 log10
1
τ λ S ~~ !!
5 log10
I τ λ 2 I d~ λ !
I λ 2 I d~ λ ! D (A1.1)

16
 D8369 − 21

A2. MODELING ABSORBANCE DATA

A2.1 The separation will typically involve multiple cases of
coelution, where more than one analyte compound can exist in
the flow cell at any given time. The absorbance for a given
number of compounds n can be written as:
n the chromatogram response (in this case by averaging over
A5 (f A
i51
1 i,ref ~ f 1 A 1,ref 1 f 2 A 2,ref 1 ... 1 f n A n,ref ! (A2.1)
where:
Ai,ref = a reference absorbance spectrum for molecule i, and
fi = a weighting factor related to the amount of compound
i present.
A2.2 The absorbances of multiple scans are summed over a
time region, or “time slice.” The relationship between this total
absorbance and the individual constituents is also given by Eq
A2.1, which then includes one term for each compound that
elutes within the time slice.
A2.3 A measured absorbance can be fit using Eq A2.1 and
a general linear least squares optimization procedure.7 The fi
are the parameters to be fit. Each of the reference spectra can
be “integrated” using the same integration filter that generated
125 nm to 240 nm), resulting in an integration factor for each
reference spectrum included in Eq A2.1. The fit fi multiplied by
the corresponding integration factors are the contributions from
each of the coeluting compounds to the chromatogram re-
sponse within the time slice.
7
Press, W. H., Flannery, B. P., Teukolsky, S. A., and Vetterling, W. T., Numerical
Recipes in C: The Art of Scientific Computing, Second Edition, Cambridge
University Press, Cambridge, UK, 1992.

APPENDIXES

(Nonmandatory Information)

X1. GASOLINE CHROMATOGRAM EXAMPLE

X1.1 As an example, the spectrum of a gasoline analysis represented in the two-dimensional chromatogram plot is seen
that has been converted to a single-valued response and in Fig. X1.1. The data report follows.

17
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example

FIG. X1.1 Chromatogram and Report Example (continued)

18
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

FIG. X1.1 Chromatogram and Report Example (continued)

19
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

FIG. X1.1 Chromatogram and Report Example (continued)

20
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

21
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

22
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

23
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

24
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

25
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

26
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

27
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

28
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

29
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

30
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

31
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

32
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

33
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

34
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

35
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

36
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

37
 D8369 − 21

FIG. X1.1 Chromatogram and Report Example (continued)

X2. EXPERIMENTAL DETERMINATION OF RELATIVE RESPONSE FACTORS

X2.1 The relative response factor for a given compound where:

may be determined from the compound’s absorption cross RRF1 = relative response factor of known compound,
section (expressed in cm2/molecule) and methane’s cross RRF2 = relative response factor of compound to be
section by calculating: determined,
A1 = total measured response area of known compound,
Σ methane MW a
RRF a 5 3 (X2.1) A2 = total measured response area of compound to be
MW methane Σa
determined,
where: M1 = percent mass of known compound in standard, and
RRFa = relative response factor for compound a, M2 = percent mass of compound to be determined in
MW = molecular weight, and standard.
Σ = absorption cross section averaged over the 125 nm X2.2.1 The standard does not have to be limited to two
to 240 wavelength region. compounds. Any number of compounds may be included, as
long as the relative response factor of one of them is known,
X2.2 The relative response factor for a given compound and all amounts are known relative to the known compound.
may be determined from a prepared standard consisting of the
compound and a second compound whose relative response
X2.3 Class-based relative response factors may be deter-
factor is known. The relative amounts of the two compounds in
mined by applying this test method to a standard having known
the standard must be known:
class-based relative concentrations. To do this, follow the
M2 A1 method procedure and calculation given in Sections 14 and 15
RRF 2 5 · RRF 1 (X2.2)
M1 A2 up to the point where class-based total response areas are

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obtained (prior to implementing Eq 3). Class-based relative
response factors are obtained from the total class response
areas and the known class percent mass concentrations of the
standard by applying Eq X2.2, except in this case all quantities
refer to class totals instead of individual compounds.
X2.3.1 If a standard consisting of known percent mass
concentrations of the hydrocarbon classes of paraffins,
isoparaffins, naphthenes, aromatics, and diaromatics is used,
this procedure will leave one of the class RRFs undetermined
(whichever one is arbitrary). The relative response factor for
the unknown class may be determined by averaging relative
response factors of a selection of individual compounds
belonging to that class by Eq X2.1. This is most easily applied
to the paraffins class. Then apply Eq X2.2 using the response
areas and relative response factor for paraffins (as RRF1) to
determine the other class-based relative response factors.
X2.3.2 If desired, the calibration procedure may use a
standard sample where the percent mass values for each carbon
number within each class are known. First, use Eq X2.1 to
calculate the RRF for one of the paraffins relative to methane.
Set that paraffin’s RRF to RRF1, its known percent mass to M1,
and its measured total area response to A1 in Eq X2.2.
Calculate each of the remaining compound class RRFs at each
carbon number by making the appropriate substitutions for M2
and A2 in Eq X2.2.

X3. ALTERNATE GC CONDITIONS WITH MICROBORE GC AND HYDROGEN CARRIER GAS (FastVHA)

X3.1 This appendix presents a modification of the GC TABLE X3.1 Chromatographic Conditions
parameters used in the test method that decreases the total Alternate Conditions
analysis time from 52.3 min to 31.9 min and eliminates the Column Dimensions Capillary, 40 m × 0.1 mm ID × 0.2 µm
film thickness
need for cryogenics. The alternate procedure uses hydrogen as Column phase Nonpolar (for example, 100 %
the carrier gas, and a high resolution microbore polydimethyl- dimethyl polysiloxane)
siloxane capillary column for separation of hydrocarbons. The Carrier Gas Hydrogen
Injector temperature 250 °C
peak separations are similar to those using the cryogenic Injection volumeA 0.1 µL
method, and are adequate to facilitate the spectral deconvolu- Split ratioA 300:1
tion of coeluting species. This modified procedure is used Column flow (constant flow) 1.2 mL ⁄min
Oven initial temperature 30 °C
widely in the refining industry as a faster alternative to Test Hold time 2.6 min
Methods D6729 or D6730, or both, for process control Oven ramp 1 50 °C
Oven temperature 1 45 °C
samples. It is also used extensively in Test Method D7900 for Hold time 3.0 min
light ends in crude analysis. The oven temperature ramp and Oven ramp 2 5 °C
column flow rate are set to ensure optimal resolution and linear Oven temperature 2 60 °C
Hold time 3 min
velocity. System performance, calibration, and pre- Oven ramp 3 9.5 °C
measurement validations utilize the same procedures and must Final oven temperature 250 °C
meet the same requirements as those in the body of the test Final Hold 0 min
Detector makeup gas pressure As Per Manufacturer’s Instructions
method. (gauge)
NOTE X3.1—At this time, because the interim test method precision and Data scan rate 5 Hz
bias information was not determined under these conditions, this appendix Detector flow cell temperature 275 °C
is included for informational purposes only. Results obtained under the Transfer line temperature 275 °C
conditions described in this appendix should not be considered to be A
Other injection volumes and split ratios may be used.
within the test method interim precision as listed in Table 5, nor
represented as such. It is envisioned that this alternate method will become
part of the complete ASTM ILS process during the first five years after
publication and move to the main body of the method. conditions, column requirements, and data acquisition require-
ments. These conditions will elute all components up to and
X3.2 Table X3.1 presents the chromatographic operating including pentadecane (n-C15).

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 D8369 − 21
X4. THE RELATIONSHIP OF MOLECULAR ABSORPTION CROSS SECTION TO RELATIVE RESPONSE FACTORS
X4.1 The Relative Response Factor (RRF) relationship to
the molecular absorption cross-section, along with a descrip-
tion of the procedure to experimentally determine RRFs is
described in Appendix X1. Additional details regarding the
application of absorption cross-sections to specific component
determinations as well as bulk property determinations in
complex hydrocarbon streams are provided.
X4.2 The absorption cross-section is the ability of a mol-
ecule to absorb a photon of a particular wavelength, or the
probability of particle-to-particle interactions causing absorp-
tion. In other words, the absorption cross-section is the
affective area of a molecule that a photon must travel through
to be absorbed. The larger the cross section, the easier it is for
a photon to be absorbed and excite bonds within that molecule.
X4.3 The absorption cross-section of a compound is a
unique molecular physical property which is defined by the
excitation of both the bonded and nonbonded electrons within
the molecule. It is uniquely described by the electronic
excitation energies (absorbed wavelengths), as well as the
oscillator strengths which corresponds to the intensity of this
absorption. The compound’s absorption cross-section is not
impacted by the power of the lamp, nor the matrix of the
sample.
X4.4 As the electron configuration is unique for each
molecule (apart from enantiomers) then all molecules exhibit
slightly different absorption responses. The two primary as-
pects of this include: (1) the shape of this absorption response
versus wavelength, and (2) the number of molecules in relation
to the measured absorption. This absorption cross-section
information, and thus the RRFs, can be stored for each
individual compound in a reference library for both qualitative
and quantitative calculations. It is also acceptable for generic
(average) reference absorption responses to be used, as classes
of molecules with similar structure have similar absorption
responses.
X4.5 From a shape perspective, the small variations within
a class are significantly less than the variations from class-to-
class. Thus, proper class determinations can be made robustly
when specific compound identifications are not required. While
these responses have small variations in their absorption shape,
the general “area under the curve” across the broad measured
40
wavelength remains remarkably similar within a class. This
allows for both the shape and response factor to be applied
effectively as averages for the analysis of bulk materials.
X4.6 This becomes more practical as the numbers of iso-
mers dramatically increases with carbon number. The variation
from these averages is more significant at lower carbon
numbers. Therefore, when speciating the components with
carbon numbers less than C12, individually determined absorp-
tion cross-sections should be used when possible.
X4.7 The quantitative aspect which drives these RRF
values, is best determined by careful determination of any
available individual compound(s) per class and per carbon
number as described in Appendix X1. In many cases, which
involve higher carbon number complex hydrocarbon streams,
like jet fuels or diesel fuels, this is not possible due to the
limited availability of individual standards. RRF changes
versus carbon number for a given class are predictable. RRF
values trend (positive or negative) within a homologous series
of a hydrocarbon class and typically asymptote as the molecu-
lar weight increases.
X4.8 The approach to establish both compound specific and
generic response factors is described by Dr. Kevin K Schug et
al in his 2016 Analytical Chemistry article.8 By comparing the
absorbance by molecule spectra and the absorbance by unit
mass when normalized to methane one can conclude, “that
while the absorbance per molecule may increase within a given
class as the molecules get heavier, the absorbance for a given
mass of compound tends to be relatively uniform.” Shown in
Fig. X4.1 are comparisons for linear alkanes and olefins.
X4.9 The RRF values per class and per carbon number are
validated through comparison to accepted voluntary consensus
board standard methods. Samples from proficiency test pro-
grams may be useful for this purpose.
X4.10 The RRF values by class and carbon number identi-
fications are shown in Fig. X4.2.
8
Walsh, P., Garbalena, M., and Schug, K. A., “Rapid analysis and time interval
deconvolution for comprehensive fuel compound group classification and speciation
using gas chromatography–vacuum ultraviolet spectroscopy,” Analytical Chemistry,
Vol 88, 17 October 2016, pp. 11130–11138, https://doi.org/10.1021/
acs.analchem.6b03226.
 D8369 − 21

FIG. X4.1 Comparisons for Linear Alkanes and Olefins

FIG. X4.1 Comparisons for Linear Alkanes and Olefins (continued)

41
 D8369 − 21

FIG. X4.1 Comparisons for Linear Alkanes and Olefins (continued)

FIG. X4.1 Comparisons for Linear Alkanes and Olefins (continued)

42
 D8369 − 21

FIG. X4.2 RRF Values by Class and Carbon Number Identifications

FIG. X4.2 RRF Values by Class and Carbon Number Identifications (continued)

43
 D8369 − 21

FIG. X4.2 RRF Values by Class and Carbon Number Identifications (continued)

FIG. X4.2 RRF Values by Class and Carbon Number Identifications (continued)

RELATED MATERIAL

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ASTM Test Method D5769 for Determination of Benzene, Toluene, and
Total Aromatics in Finished Gasolines by Gas Chromatography/Mass
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through n-Nonane by Capillary Gas Chromatography

44
 D8369 − 21
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