ASTM D8302-20

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: D8302 − 20
Standard Test Method for
Determination of Cycloparaffin Content in Saturated ATJ-
SPK Jet Fuel Gas Chromatography
This standard is issued under the fixed designation D8302; 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 D7566 Specification for Aviation Turbine Fuel Containing
Synthesized Hydrocarbons
1.1 This test method covers the determination of cyclopar-
D7372 Guide for Analysis and Interpretation of Proficiency
affin content by gas chromatography of the saturatedATJ-SPK
Test Program Results
jet fuel as specified in Specification D7566, section A5.4.1,
E355 Practice for Gas Chromatography Terms and Relation-
derived from isobutanol and follows the fuel fingerprint
ships
described in the Annex of this test method.
E594 Practice for Testing Flame Ionization Detectors Used
1.2 The working range for the test method is for cyclopar-
in Gas or Supercritical Fluid Chromatography
affin content in the range of 1 % to 15 % by mass.
3. Terminology
1.3 The test method has an interim precision and will be
updated once an extended ILS is conducted.
3.1 This test method references common gas chromato-
graphic procedures, terms, and relationships which may be
1.4 This standard does not purport to address all of the
found in Practices E355 and E594.
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
3.2 Definitions:
priate safety, health, and environmental practices and deter-
3.2.1 paraffıns, n—saturated, non-cyclic hydrocarbons.
mine the applicability of regulatory limitations prior to use.
3.3 Abbreviations:
1.5 This international standard was developed in accor-
3.3.1 ATJ-SPK—alcohol-to-jet synthetic paraffinic kerosene
dance with internationally recognized principles on standard-
3.3.2 ASTM—American Society for Testing and Materials
ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom-
3.3.3 FID—flame ionization detector
mendations issued by the World Trade Organization Technical
3.3.4 GC/MS—gas chromatograph mass spectrometer
Barriers to Trade (TBT) Committee.
3.3.5 IPC—identified paraffin concentration
3.3.6 m/z—molecular mass to charge ratio of an ion
2. Referenced Documents
3.3.7 PTP—proficiency testing programs
2.1 ASTM Standards:
D2425 Test Method for Hydrocarbon Types in Middle Dis-
3.3.8 QC—quality control
tillates by Mass Spectrometry
4. Summary of Test Method
D6299 Practice for Applying Statistical Quality Assurance
and Control Charting Techniques to Evaluate Analytical
4.1 A representative aliquot of ATJ-SPK jet fuel is intro-
Measurement System Performance
duced into a gas chromatograph equipped with a 5 % phenyl-
D6300 Practice for Determination of Precision and Bias
methylpolysiloxane bonded phase capillary column. Carrier
Data for Use in Test Methods for Petroleum Products,
gas transports the vaporized aliquot through the column where
Liquid Fuels, and Lubricants
the components are separated by the chromatographic process.
Components are sensed by a flame ionization detector as they
elute from the column in boiling point order. The detector
This test method is under the jurisdiction of ASTM Committee D02 on
signal is processed by an electronic data acquisition system.
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
The paraffins are identified by comparing their retention times
Subcommittee D02.04 on Hydrocarbon Analysis.
to the ones reported in the method. Identification of the
Current edition approved July 1, 2020. Published July 2020. DOI: 10.1520/
D8302-20.
paraffinshasbeenpreviouslyperformedbyanalyzingreference
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
samples and standards by mass spectrometry under conditions
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
as indicated in the Annex. The concentrations of all compo-
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. nents are determined in mass percent area by normalization of
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D8302 − 20
the peak areas. The cycloparaffin content is determined as 6.3 Column—This test method utilizes a fused silica open
100 % percent paraffins. tubular column with 5 %-Phenyl-methylpolysiloxane bonded
(cross-linked) phase. A 30 m by 0.32 mm with a 0.25 µm film
5. Significance and Use
thickness was used to develop this method and all peak
identificationsdescribedinthismethodwereobtainedwiththis
5.1 This test method applies specifically to theATJ-SPK jet
column. Any column with equivalent polarity, improved chro-
fuel as specified in Specification D7566, section A5.4.1,
matographic efficiency and selectivity as described in 6.3.1
derived from isobutanol and follows the fuel fingerprint
may be used as long as the compounds of interest are readily
described in the annex of this test method. It may not apply to
identified.
other types of ATJ-SPK fuels.
6.4 Electronic Data Acquisition System—Any electronic
5.2 Table A2.2 in Specification D7566 prescribes cyclopar-
data acquisition and integration device used for quantification
affin concentration be a maximum of 15 % by mass.
of these analyses shall meet or exceed these minimum require-
5.3 Due to the nature of the chemical composition of
ments:
ATJ-SPK jet fuel, standard analysis of the sample by Test
6.4.1 Normalized percent calculation based on peak area
Method D2425 for cycloparaffin content may yield a higher
and using response factors,
concentration of cycloparaffins than are actually present in the
6.4.2 Identification of individual components based on
sample.
standards,
5.4 This method alleviates the potential for overestimating
6.4.3 Noise and spike rejection capability,
the cycloparaffin concentration by measuring the concentration
6.4.4 Non-resolved peaks separated by perpendicular drop
of identified paraffins. Any remaining unidentified compounds
or tangential skimming as needed.
are classified as potential cycloparaffins.
7. Reagents and Materials
6. Apparatus
7.1 Carrier Gas, helium, with a minimum purity of
6.1 Gas Chromatograph, capable of operating at the condi-
99.95 % mol. Oxygen removal systems and gas purifiers are
tions listed in Table 1. A heated flash vaporizing injector
recommended. (Warning—Helium, compressed gas under
designed to provide a linear sample split injection (for
high pressure.) Hydrogen carrier gas was not tested during
example, 200:1) is required for proper sample introduction.
development of this test method.
Carrier gas controls shall be of adequate precision to provide
reproducible column flows and split ratios in order to maintain
7.2 Detector Gases, hydrogen, air, and nitrogen. The mini-
analytical integrity. Pressure control devices and gauges shall
mum purity of the gases used should be 99.95 % mol for the
be designed to attain the linear velocity required in the column
hydrogen and nitrogen. The air should be hydrocarbon-free
used.Ahydrogen flame ionization detector with associated gas
grade. Gas purifiers are recommended for the detector gases.
controls and electronics, designed for optimum response with
(Warning—Hydrogen, extremely flammable gas under high
open tubular (capillary) columns, is required.
pressure.) (Warning—Air and nitrogen, compressed gases
under high pressure.)
6.2 Sample Introduction—Manual or automatic liquid sy-
ringe sample injection to the splitting injector is employed.
7.3 Standards for Calibration and Identification—Standards
Devices capable of 0.1 µL to 0.5 µL injections are suitable. It
of components to be analyzed are required for establishing
should be noted that inadequate splitter design, poor injection
identification by retention time. These standards shall be of
technique and overloading the column may result in poor
highest purity, preferably ≥98 %. (Warning—These materials
resolution and quantification.
are flammable and may be harmful or fatal if ingested or
inhaled.)
7.3.1 2, 2, 4-trimethylpentane, ≥99 % purity (Warning—
TABLE 1 Typical Operating Conditions
Flammableandmaybeharmfulorfatal,ifingestedorinhaled.)
Column Temperature Program
7.3.2 2,3,4-trimethylpentane, ≥98 % purity (Warning—
Column Length 30 m
Initial Temperature 50 °C
Flammableandmaybeharmfulorfatal,ifingestedorinhaled.)
Initial Hold Time 2 min
7.3.3 2,2,4,6,6-pentamethylheptane, ≥98 % purity
Program Rate 10 °C ⁄min
(Warning—Flammable and may be harmful or fatal, if in-
Final Temperature 290 °C
Final Hold Time 0 min
gested or inhaled.)
Injector
7.3.4 2,2,4,4,6,8,8-Heptamethylnonane, ≥98 % purity
Temperature 200 °C
Split Ratio 200:1 (Warning—Flammable and may be harmful or fatal, if in-
Sample Size 0.1 µL
gested or inhaled.)
Detector
Type Flame Ionization
Fuel Gas Hydrogen (35 mL ⁄min) 8. Sampling
Oxidizing Gas Air (350 mL ⁄min)
Make-up Gas Nitrogen (12.6 mL ⁄min) 8.1 Transfer an aliquot of the sample to be analyzed into a
Carrier Gas
vial and seal. Inject the test sample directly into the gas
Type Helium
chromatograph, either manual or preferably using an automatic
Flow Rate 2.5 mL ⁄min
syringe injection.
D8302 − 20
9. Preparation of Apparatus identified paraffin peaks. Subtract the result from 100 to
determine maximum potential cycloparaffin concentration:
9.1 Install and condition column in accordance with manu-
facturer’sorsupplier’sinstructions.Checkforleaksthroughout Percent of Identified Paraffin Concentration ~IPC!
the system and if leaks are found, tighten or replace fittings
5 ~Area of Paraffinic Identified Peaks/Total Peak Area!*100 (1)
before proceeding.
Maximum percent potential cycloparaffin concentration 5 100 2 IPC
9.2 Adjust the operating conditions of the gas chromato-
(2)
graph in accordance to Table 1 (6.4.4) and allow the system to
13. Quality Control of Test Method Performance
equilibrate.
13.1 Confirm the test method performance via regular
10. Calibration and Standardization
testing of quality control (QC) sample(s) following the guid-
10.1 Standard Identification—Determine the retention times ance in Practice D6299.
of 2,2,4-trimethylpentane, 2,3,4-trimethylpentane, 2,2,4,6,6- 13.1.1 The QC material should be representative of the
pentamethylheptane, and 2,2,4,4,6,8,8-heptamethylnonane. samples analyzed routinely.
10.2 Unidentified Paraffın Peaks—Additional small peaks 13.2 Use of a reference fuel or participation in appropriate
surrounding the known 2,2,4,6,6-pentamethylheptane and 2,2, proficiency testing programs (PTP), or both, is recommended
4,4,6,8,8-heptamethylnonane standard peaks have been deter- for monitoring performance relative to industry and to verify
mined to be paraffinic based on their mass fragmentation
that all compounds are identified correctly and that the instru-
patterns from GC/MS analysis. Although the exact structures ment is properly optimized. Follow Practice D7372 for PTP.
of these peaks have not been identified or confirmed by
14. Report
analysis of purchased standards, the peaks have been desig-
nated as paraffinic and are quantitated as such. 14.1 Report the maximum potential cycloparaffin concen-
tration to the nearest 0.01 % by mass, and reference this test
10.2.1 Additional
...