ASTM D5443-23

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Designation: D5443 − 14 (Reapproved 2018) D5443 − 23
Standard Test Method for
Paraffin, Naphthene, and Aromatic Hydrocarbon Type
Analysis in Petroleum Distillates Through 200 °C by Multi-
Dimensional Gas Chromatography
This standard is issued under the fixed designation D5443; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope Scope*
1.1 This test method covers the determination of paraffins, naphthenes, and aromatics by carbon number in low olefinic
hydrocarbon streams having final boiling points of 200 °C or less. Hydrocarbons with boiling points greater than 200 °C and less
than 270 °C are reported as a single group. Olefins, if present, are hydrogenated and the resultant saturates are included in the
paraffin and naphthene distribution. Aromatics boiling at C and above are reported as a single aromatic group.
1.2 This test method is not intended to determine individual components except for benzene and toluene that are the only C and
C aromatics, respectively, and cyclopentane that is the only C naphthene. The lower limit of detection for a single hydrocarbon
7 5
component or group is 0.05 % by mass.
1.3 This test method is applicable to hydrocarbon mixtures including virgin, catalytically converted, thermally converted,
alkylated and blended naphtha.
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.4.1 The abbreviation for SI unit “coulomb” is “C”.
1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of
the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of
regulatory limitations prior to use. Specific precautionary statements are given in Section 7 and Table 1.
1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of
regulatory limitations prior to use. Specific precautionary statements are given in Section 8 and Table 1.
1.6 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
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 Oct. 1, 2018March 1, 2023. Published November 2018March 2023. Originally approved in 1993. Last previous edition approved in 20142018
as D5443 – 14.D5443 – 14 (2018). DOI: 10.1520/D5443-14R18.10.1520/D5443-23.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
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TABLE 1 Hydrocarbon Test Mixture
Hydrocarbons Warning
Cyclopentane (Warning—Extremely Flammable. Harmful if inhaled.)
Pentane (Warning—Extremely Flammable. Harmful if inhaled.)
Cyclohexane (Warning—Extremely Flammable. Harmful if inhaled.)
2,3-Dimethylbutane (Warning—Extremely Flammable. Harmful if inhaled.)
Hexane (Warning—Extremely Flammable. Harmful if inhaled.)
1-Hexene (Warning—Extremely Flammable. Harmful if inhaled.)
Methylcyclohexane (Warning—Extremely Flammable. Harmful if inhaled.)
4-Methyl-1-hexene (Warning—Extremely Flammable. Harmful if inhaled.)
Heptane (Warning—Flammable. Harmful if inhaled.)
1,cis-2-Dimethylcyclohexane (Warning—Extremely Flammable. Harmful if
inhaled.)
2,2,4-Trimethylpentane (iso-octane) (Warning—Flammable. Harmful if inhaled.)
Octane (Warning—Flammable. Harmful if inhaled.)
1,cis-2,cis-4-Trimethylcyclohexane (Warning—Flammable. Harmful if inhaled.)
Nonane (Warning—Flammable. Harmful if inhaled.)
Decane (Warning—Flammable. Harmful if inhaled.)
Undecane (Warning—Flammable. Harmful if inhaled.)
Dodecane (Warning—Flammable. Harmful if inhaled.)
Benzene (Warning—Extremely Flammable. Harmful if inhaled.)
Methylbenzene (Toluene) (Warning—Flammable. Harmful if inhaled.)
trans-Decahydronaphthalene (Decalin) (Warning—Flammable. Harmful if in-
haled.)
Tetradecane (Warning—Harmful if inhaled.)
Ethylbenzene (Warning—Extremely Flammable. Harmful if inhaled.)
1,2-Dimethylbenzene (o-Xylene) (Warning—Extremely Flammable. Harmful if
inhaled.)
Propylbenzene (Warning—Extremely Flammable. Harmful if inhaled.)
1,2,4-Trimethylbenzene (Warning—Extremely Flammable. Harmful if inhaled.)
1,2,3-Trimethylbenzene (Warning—Extremely Flammable. Harmful if inhaled.)
1,2,4,5-Tetramethylbenzene (Warning—Flammable. Harmful if inhaled.)
Pentamethylbenzene (Warning—Harmful if inhaled.)
2. Referenced Documents
2.1 ASTM Standards:
D4057 Practice for Manual Sampling of Petroleum and Petroleum Products
D4175 Terminology Relating to Petroleum Products, Liquid Fuels, and Lubricants
D4307 Practice for Preparation of Liquid Blends for Use as Analytical Standards
D5134 Test Method for Detailed Analysis of Petroleum Naphthas through n-Nonane by Capillary Gas Chromatography
D6839 Test Method for Hydrocarbon Types, Oxygenated Compounds, Benzene, and Toluene in Spark Ignition Engine Fuels by
Multidimensional Gas Chromatography
E355 Practice for Gas Chromatography Terms and Relationships
3. Terminology
3.1 Definitions:
3.1.1 For definitions of terms used in this test method, refer to Terminology D4175 and Practice E355.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 naphthene(s), n—cycloparaffin(s).
4. Summary of Test Method
4.1 A representative sample is introduced into a gas chromatographic system containing a series of columns and switching valves.
As the sample passes through a polar column, the polar aromatic compounds, bi-naphthenes, and high boiling (>200 °C) paraffins
and naphthenes are retained. The fraction not retained elutes to a platinum column, that hydrogenates olefins, if present, in this
fraction, and then to a molecular sieve column which performs a carbon number separation based on molecular structure, that is,
naphthenes and paraffins. The fraction remaining on the polar column is further divided into three separate fractions that are then
separated on a non-polar column by boiling point. Eluting compounds are detected by a flame ionization detector.
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.
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4.2 The mass concentration of each group is determined by the multiplication of detected peak areas by flame ionization detector
response factors and normalization to 100 %.
4.3 This test method provides limited identification of individual hydrocarbon components. Test Method D5134 may be used to
obtain speciation of a number of individual compounds. For samples containing olefins, Test Method D6839 provides carbon
number distributions of hydrocarbon types (PIONA).
5. Significance and Use
5.1 A knowledge of the composition of hydrocarbon refinery streams is useful for process control and quality assurance.
5.2 Aromatics in gasoline are soon to be limited by federal mandate. This test method can be used to provide such information.
6. Interferences
6.1 Chemicals of a non-hydrocarbon composition may elute within the hydrocarbon groups, depending on their polarity, boiling
point, and molecular size. Included in this group are ethers (for example, methyl-tertiary butyl ether) and alcohols (for example,
ethanol).
7. Apparatus
7.1 Chromatograph—A gas chromatograph capable of isothermal operation at 130 °C 6 0.1 °C. The gas chromatograph must
contain the following:
7.1.1 A heated flash vaporization sample inlet system capable of operation in a splitless mode.
7.1.2 Associated gas controls with adequate precision to provide reproducible flows and pressures.
7.1.3 A flame ionization detection system optimized for use with packed columns and capable of the following:
Isothermal temperature operation 150 °C to 170 °C
Sensitivity >0.015 C/g
−12
Minimum detectability 5 × 10 g carbon/s
Linearity >10
Some instruments will produce a non-linear response for benzene, above approximately 5.5 % by mass, and for toluene above
approximately 15 % by mass. The linearity of these components above these concentrations must be verified with appropriate
blends. Where non-linearity has been shown to exist, samples, that contain no higher than C , can be analyzed if the sample is
diluted with n-C and the instrument is equipped with a prefractionating column. The sample may also be diluted with a
component that is not present in the sample and this component will then not be included in the normalized report.
7.2 Sample Introduction System—Manual or automatic liquid sample system operated in a splitless mode. Although this test
method is intended primarily for use with syringe sample injection, automatic sampling valves have also been found satisfactory.
Devices capable of a reproducible injection volume of 0.1 μL to 0.5 μL are suitable. The sample introduction system must be
capable of heating the sample to a temperature that ensures total sample vaporization. A temperature range of 120 °C to 180 °C
has been found suitable.
7.3 Electronic Data Acquisition System—The data acquisition and integration device used for detection and integration must meet
or exceed the following specifications:
7.3.1 Capacity for at least 75 peaks for each analysis,
7.3.2 Normalized area percent calculation,
7.3.3 Noise and spike rejection capability,
7.3.4 Sampling rates for fast (<2 s) peaks,
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TABLE 2 Typical Column Specifications
Column Type
Specification
Polar Non-Polar Tenax Molsieve Platinum
Column length, m 3 4 0.16 to 0.18 1.8 0.002 to 0.06
Column inside diameter, mm 2.0 to 2.1 1.8 to 2.0 2.5 1.6 to 2.0 1.6
A A
Liquid phase OV-275 OV-101 . . .
Percent liquid phase 30 4–5 . . .
B B
Support material Chromasorb Chromasorb . . .
PAW WAW . . .
3 C ,D
Packing material . . Tenax Molecular sieve 13X .
Mesh size 60/80 80/100 80/100 . .
A
OV-101 and OV-275 are registered trademarks of Ohio Valley Specialty Chemical Co., 115 Industry Rd., Marietta, OH 45750.
B
Chromasorb is a registered trademark of World Minerals, Corp., Santa Barbara, CA.
C
Sodium form of molecular sieve 13X.
D
May also contain a mix of molecular sieves 13X and 5A to separate normal and iso-paraffins.
7.3.5 Peak width detection for narrow and broad peaks, and
7.3.6 Perpendicular drop and tangent skimming as required.
7.4 Independent Temperature Control—This test method requires the temperature control of five columns, column switching
valves and sample lines. The columns consist of polar, non-polar, Tenax , platinum, and molecular sieve columns. The
specifications for these columns are listed in Table 2. The polar column, non-polar column, column switching valves, and sample
lines require isothermal operation at a temperature equivalent to the temperature of the gas chromatograph oven. These components
may be located in the gas chromatograph oven. The Tenax column, platinum column, and molecular sieve column require operation
at temperatures other than the gas chromatograph oven temperature. These columns may be temperature controlled by any means
that will meet the specifications in Table 2.
7.4.1 Ability to control the temperature of the Tenax column within a range from 60 °C to 280 °C, with a tolerance of 65 °C at
any point. The time required to heat this column between any two points must be no more than 1 min. The time required to cool
this column between any two points must be no more than 5 min,
7.4.2 Ability to control the temperature of the molecular sieve column within a range from 100 °C and 490 °C, with a tolerance
of 610 °C at any point. The time required to heat this column between any two points must be no more than 10 min. The time
required to cool this column from 450 °C to 100 °C must be no more than 15 min, and
7.4.3 Ability to control the platinum column within a temperature range of 170 °C and 350 °C. During routine analysis, this
column is operated within a temperature range of 170 °C to 220 °C.
NOTE 1—Newer analyzers may have updated hardware and/or separation columns types and traps dimensions. Precision using using newer hardware
configurations or conditions have not been studied by ASTM. The precision listed in this method was obtained with hardware described in this test
method.
8. Materials
8.1 Carrier Gases—For carrier gases, it is recommended to install commercial active oxygen scrubbers and water dryers, such as
molecular sieves, ahead of the instrument to protect the system’s chromatographic columns. Follow supplier instructions in the use
of such gas purifiers and replace as necessary.
8.1.1 Hydrogen, 99.995 % by mol minimum purity, <0.1 μL ⁄L H O. (Warning—Extremely flammable gas under high pressure.)
8.1.2 Helium, 99.995 % by mol minimum purity, <0.1 μL/L H O. (Warning—Compressed gas under high pressure.)
8.2 Detector Gases:
8.2.1 Hydrogen, 99.99 % by mol minimum purity. (Warning—Extremely flammable gas under high pressure.)
Tenax is a registered trademark of AKZO, Velperweg 76, P.O. Box 9300, 6800 SB Arnhem, The Netherlands.
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8.2.2 Air, less than 10 μL ⁄L each of total hydrocarbons and water. (Warning—Compressed gas under high pressure.)
8.3 Valve Actuation Gas—This test method permits the use of any type of valve switching or valve actuation. When pneumatic
valves are used, air of any grade that will result in no water condensation or will not introduce oil or other contaminates in the
switching valves may be used. Air from a piston operated compressor equipped with a water and oil separator has been found
suitable. Column switching valves that do not require air to operate do not have this air requirement.
8.4 Columns—Five columns, as described in Table 2. These column specifications are to be considered as guidelines and have
been found to be acceptable. Other materials or combinations of materials may also provide acceptable performance. The
suitability of each column is determined by test criteria as defined in Section 89.
NOTE 2—It is not the intention of this test method to include detailed column preparation steps. Columns may be prepared in any way that follows accepted
safety practices and results in columns that will meet the performance requirements of Section 910.
8.5 Valves—This test method uses valves for column switching and flow switching. Any commercially available valves may be
used that are intended for, or adapted for use in gas chromatography that meet the following specifications:
8.5.1 The column switching valves are generally installed in the gas chromatograph oven. These valves must be capable of
continuous operation at the operating temperature of the GC oven.
8.5.2 Materials used in the construction of the valves must be unreactive to hydrocarbons present in the sample under analysis
conditions. Stainless steel, PFA, and vespel materials have been found suitable.
8.5.3 Valves must be sized such that they offer little restriction to carrier gas flow under the analysis conditions defined in this test
method.
8.5.4 Care must be taken to prevent the introduction of any form of foreign material or contaminant into the valve that may
adversely affect its performance.
8.6 Hydrocarbon Test Mixture—A quantitative synthetic mixture of pure hydrocarbons, an example of which is identified in Table
1, is used to tune the instrument analysis conditions and establish that the instrument is performing within specifications. Individual
hydrocarbon components, in addition to those listed in Table 1, may be used to aid in the analysis. The concentration level of each
component in the hydrocarbon test mixture is not critical as long as the concentration is accurately known. Percentage ranges from
1.0 % to 6.0 % by mass have been found suitable. Impurities in the individual components may have an adverse effect on the
quantitative aspect of the analysis. If an impurity is of the same carbon number and basic molecular structure as the main
component itself, it will be correctly grouped and quantitated within the group. As an example, isobutylcyclopentane and
isopropylcyclohexane will both be determined as C naphthenes. Each of the individual hydrocarbon components used for this test
mixture must have a minimum purity level of 99 % by mol. Refer to Practice D4307 for instructions on the preparation of liquid
blends for use as analytical standards.
8.7 Gas Flows and Pressures:
8.7.1 Carrier Gases:
8.7.1.1 The helium carrier gas through the injection port, polar column, platinum column and molecular sieve column is flow
controlled. Flow rates of 16 mL/min to 23 mL/min have been found suitable. A helium supply pressure of 620 kPa (90 psi) has
been found suitable to meet the helium flow requirement. The helium carrier gas flow will be referred to as the “A” flow within
this test method.
8.7.1.2 The helium carrier gas used as the makeup gas when the polar column is in stop flow is set to the same flow rate as the
helium carrier gas through the injection port.
8.7.1.3 The hydrogen carrier gas flow through the Tenax column and non-polar column is flow controlled. Flow rates of
12 mL ⁄min to 17 mL/min have been found suitable. A hydrogen supply pressure of 517 kPa (75 psi) has been found suitable to
meet the hydrogen flow requirements. The hydrogen carrier gas flow will be referred to as the “B” flow within this test method.
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8.7.1.4 The hydrogen flow to the platinum column is flow controlled. Flow rates of 10 mL ⁄min to 15 mL/min have been found
suitable.
8.7.2 Detector Gases—The flow rates of the air and hydrogen, as oxidant and fuel gases for the flame ionization detector, must
be set according to the instrument manufacturer’s instructions.
8.7.3 Valve Actuation Gases—Pneumatic valves require air delivery at pressures and flows adequate to ensure correct actuation.
When pneumatic valves are used for this test method, air pressure and flow must be provided in accordance with the valve
manufacturer’s instructions.
NOTE 3—Some manufacturers have reported successful execution of this test method using purified nitrogen in lieu of helium as a carrier gas. The
precision listed in this test method is based on helium as a carrier gas. Precision and bias performance using purified nitrogen relative to helium has not
been studied by ASTM.
9. System Description
9.1 Commercial instruments are available that meet the specifications of this test method. Additional operating instructions are
included in the operating and maintenance manuals for these instruments. The figures in this test method are applicable to these
systems.
9.1.1 Fig. 1 and Fig. 2 illustrate typical instrument configurations that use different column valve switching techniques. This test
method allows use of either configuration.
9.1.2 Figs. 3-13 illustrate the system flow configurations during the column test and sample analysis phases of this test method.
9.1.3 Table 3 and Table 4 list the conditions that apply during the column test and sample analysis phases for the instrument
configuration in Fig. 1.
9.1.4 Table 5 and Table 6 list the conditions that apply during the column test and sample analysis phases for the instrument
configuration in Fig. 2.
9.2 The polar column separates the sample into four fractions. The first three fractions are fore-flushed through the polar column
and the last is back-flushed. Upon completion of each elution cycle, the flow through the column is stopped to maintain the relative
position of non-eluted components within the column. For the purpose of simplicity, the three fore-flushes of the polar column will
be called the “A,” “B,” and “C” cuts, respectively. The length of time associated with each cut will be called the “A,” “B,” and
“C” times, respectively. These times are independent of each other and are a function of instrument configuration, column
performance and carrier gas flow conditions.
10. Preparation of Apparatus
10.1 Place the gas chromatograph in service in accordance with the manufacturer’s instructions. The initial settings listed in Table
3 and Table 4 have been found suitable for slider valve type instruments. The initial settings listed in Table 5 and Table 6 have
been found suitable for rotary valve type instruments. Variances in
...