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: D5134 − 21

Standard Test Method for

Detailed Analysis of Petroleum Naphthas through n-Nonane
by Capillary Gas Chromatography1
This standard is issued under the fixed designation D5134; 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.

INTRODUCTION

Despite the many advances in capillary gas chromatography instrumentation and the remarkable
resolution achievable, it has proven difficult to standardize a test method for the analysis of a mixture
as complex as petroleum naphtha. Because of the proliferation of numerous, similar columns and the
endless choices of phase thickness, column internal diameter, length, etc., as well as instrument
operating parameters, many laboratories use similar but not identical methods for the capillary GC
analysis of petroleum naphthas. Even minute differences in column polarity or column oven
temperature, for example, can change resolution or elution order of components and make their
identification an individual interpretive process rather than the desirable, objective application of
standard retention data. To avoid this, stringent column specifications and temperature and flow
conditions have been adopted in this test method to ensure consistent elution order and resolution and
reproducible retention times. Strict adherence to the specified conditions is essential to the successful
application of this test method.

1. Scope* 1.5 Detailed hydrocarbon components in olefin containing

samples may be determined by DHA Test Methods D6729,
1.1 This detailed hydrocarbon analysis (DHA) test method
D6730, or D6733.
covers the determination of hydrocarbon components paraffins,
naphthenes, and monoaromatics (PNA) of petroleum naphthas 1.6 The values stated in SI units are to be regarded as
as enumerated in Table 1. Components eluting after n-nonane standard. No other units of measurement are included in this
(bp 150.8 °C) are determined as a single group. standard.
1.7 This standard does not purport to address all of the
1.2 This test method is applicable to olefin-free (<2 % safety concerns, if any, associated with its use. It is the
olefins by liquid volume) liquid hydrocarbon mixtures includ- responsibility of the user of this standard to establish appro-
ing virgin naphthas, reformates, and alkylates. Olefin content priate safety, health, and environmental practices and deter-
can be determined by Test Method D1319 or D6839. The mine the applicability of regulatory limitations prior to use.
hydrocarbon mixture must have a 98 % point of 250 °C or less Specific warning statements are given in Section 8.
as determined by Test Method D3710 or D7096 or equivalent. 1.8 This international standard was developed in accor-
1.3 Components that are present at the 0.05 % by mass level dance with internationally recognized principles on standard-
or greater can be determined. ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom-
1.4 This test method may not be completely accurate for mendations issued by the World Trade Organization Technical
PNA above carbon number C7; Test Method D5443 or D6839 Barriers to Trade (TBT) Committee.
may be used to verify or complement the results of this test
2. Referenced Documents
method for carbon numbers >C7.
2.1 ASTM Standards:2
D1319 Test Method for Hydrocarbon Types in Liquid Petro-
1
leum Products by Fluorescent Indicator Adsorption
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
2
Subcommittee D02.04.0L on Gas Chromatography Methods. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Dec. 1, 2021. Published December 2021. Originally contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
approved in 1990. Last previous edition approved in 2017 as D5134 – 13 (2017). Standards volume information, refer to the standard’s Document Summary page on
DOI: 10.1520/D5134-21. the ASTM website.

*A Summary of Changes section appears at the end of this standard

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

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TABLE 1 Typical Retention Characteristics of Naphtha Components
NOTE 1—The abbreviations N and P refer to unidentified naphthenes and paraffins respectively.
Adjusted Retention Kovats Retention
Compound Retention Time, min Linear Retention Index
Time, min Index @ 35 °C
Methane 3.57 0.00 100.0 ...
Ethane 3.65 0.08 200.0 ...
Propane 3.84 0.27 300.0 ...
Isobutane 4.14 0.57 367.3 ...
n-Butane 4.39 0.82 400.0 ...
2,2-Dimethylpropane 4.53 0.96 415.5 ...
Isopentane 5.33 1.76 475.0 ...
n-Pentane 5.84 2.27 500.0 ...
2,2-Dimethylbutane 6.81 3.24 536.2 ...
Cyclopentane 7.83 4.26 564.1 ...
2,3-Dimethylbutane 7.89 4.32 565.5 ...
2-Methylpentane 8.06 4.49 569.5 ...
3-Methylpentane 8.72 5.15 583.4 ...
n-Hexane 9.63 6.06 600.0 ...
2,2-Dimethylpentane 11.22 7.65 624.2 ...
Methylcyclopentane 11.39 7.82 626.5 ...
2,4-Dimethylpentane 11.68 8.11 630.3 ...
2,2,3-Trimethylbutane 12.09 8.52 635.4 ...
Benzene 13.29 9.72 649.1 ...
3,3-dimethylpentane 13.84 10.27 654.8 ...
Cyclohexane 14.19 10.62 658.3 ...
2-Methylhexane 15.20 11.63 667.8 ...
2,3-Dimethylpentane 15.35 11.78 669.1 ...
1,1-Dimethylcyclopentane 15.61 12.04 671.4 ...
3-Methylhexane 16.18 12.61 676.2 ...
cis-1,3-Dimethylcyclopentane 16.88 13.31 681.8 ...
trans-1,3-Dimethylcyclopentane 17.22 13.65 684.4 ...
3-Ethylpentane 17.44 13.87 686.1 ...
trans-1,2-Dimethylcyclopentane 17.57 14.00 687.0 ...
2,2,4-Trimethylpentane 17.80 14.23 688.7 ...
n-Heptane 19.43 15.86 700.0 ...
Methylcyclohexane + cis-1,2-Dimethylcyclopentane 22.53 18.96 718.6A ...
1,1,3-Trimethylcyclopentane + 2,2-Dimethylhexane 23.05 19.48 721.4A ...
Ethylcyclopentane 24.59 21.02 729.3A ...
2,5-Dimethylhexane + 2,2,3-Trimethylpentane 25.12 21.55 731.9A ...
2,4-Dimethylhexane 25.47 21.90 733.5A ...
1,trans-2,cis-4-Trimethylcyclopentane 26.43 22.86 738.0A ...
3,3-Dimethylhexane 26.79 23.22 739.6A ...
1,trans-2,cis-3-Trimethylcyclopentane 28.01 24.44 744.9A ...
2,3,4-Trimethylpentane 28.70 25.13 747.8A ...
Toluene + 2,3,3-Trimethylpentane 29.49 25.92 751.1A 730.2B
1,1,2-Trimethylcyclopentane 31.21 27.64 ... 741.7B
2,3-Dimethylhexane 31.49 27.92 ... 743.6B
2-Methyl-3-ethylpentane 31.69 28.12 ... 744.9A
2-Methylheptane 33.06 29.49 ... 754.1B
4-Methylheptane + 3-Methyl-3-ethylpentane 33.34 29.77 ... 756.0B
3,4-Dimethylhexane 33.49 29.92 ... 757.0B
1,cis-2,trans-4-Trimethylcyclopentane + 1,cis-2,cis-4-Trimethylcyclopentane 33.73 30.16 ... 758.6B
cis-1,3-Dimethylcyclohexane 34.45 30.88 ... 763.4B
3-Methylheptane + 1,cis-2,trans-3-Trimethylcyclopentane 34.64 31.07 ... 764.7B
3-Ethylhexane + trans-1,4-Dimethylcyclohexane 34.83 31.26 ... 766.0B
1,1-Dimethylcyclohexane 35.81 32.24 ... 772.5B
2,2,5-Trimethylhexane + trans-1,3-Ethylmethylcyclopentane 36.75 33.18 ... 778.8B
cis-1,3-Ethylmethylcyclopentane 37.14 33.57 ... 781.4B
trans-1,2-Ethylmethylcyclopentane 37.39 33.82 ... 783.1B
2,2,4-Trimethylhexane + 1,1-Ethylmethylcyclopentane 37.68 34.11 ... 785.1B
trans-1,2-Dimethylcylohexane 38.14 34.57 ... 788.1B
1,cis-2,cis-3-Trimethylcyclopentane 39.21 35.64 ... 795.3B
trans-1,3-Dimethylcyclohexane + cis-1,4-Dimethylcyclohexane 39.54 35.97 ... 797.5
n-Octane 39.91 36.34 ... 800.0
Isopropylcyclopentane + 2,4,4-Trimethylhexane 40.76 37.19 ... 805.7
Unidentified C9-Naphthene 40.88 37.31 ... 806.5
Unidentified C8-Naphthene 41.52 37.95 ... 810.8
Unidentified C9-Naphthene 41.88 38.31 ... 813.2
cis-1,2-Ethylmethylcyclopentane + 2,3,5-Trimethylhexane 42.55 38.98 ... 817.7
2,2-Dimethylheptane 43.20 39.63 ... 822.0
cis-1,2-Dimethylcyclohexane 43.43 39.86 ... 823.6
2,2,3-Trimethylhexane + 9N 43.76 40.19 ... 825.8
2,4-Dimethylheptane 43.88 40.31 ... 826.6
4,4-Dimethylheptane + 9N 44.09 40.52 ... 828.0
Ethylcyclohexane + n-Propylcyclopentane 44.36 40.79 ... 829.8
2-Methyl- 4-Ethylhexane 44.74 41.17 ... 832.4

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TABLE 1 Continued
Adjusted Retention Kovats Retention
Compound Retention Time, min Linear Retention Index
Time, min Index @ 35 °C
2,6-Dimethylheptane + 9N 44.95 41.38 ... 833.8
1,1,3-Trimethylcyclohexane 45.21 41.64 ... 835.5
Unidentified C9-Naphthene 45.56 41.99 ... 837.8
2,5-Dimethylheptane + 9P 45.92 42.35 ... 840.3
3,5-Dimethylheptane + 3,3-Dimethylheptane + N 46.09 42.52 ... 841.4
Unidentified C9-Naphthene 46.31 42.74 ... 842.9
Unidentified C9-Naphthene 46.55 42.98 ... 844.5
Ethyl Benzene 47.15 43.58 ... 848.5
Unidentified C9-Naphthene 47.37 43.80 ... 850.0
Unidentified Naphthene + 2,3,4-Trimethylhexane 47.53 43.96 ... 851.0
Unidentified Naphthenes 47.78 44.21 ... 852.7
Unidentified Naphthene + Paraffin 48.13 44.56 ... 855.1
m-Xylene 48.49 44.92 ... 857.5
p-Xylene 48.63 45.06 ... 858.4
2,3-Dimethylheptane 48.93 45.36 ... 860.4
3,4-DimethylheptaneC + N 49.10 45.53 ... 861.6
3,4-DimethylheptaneC 49.29 45.72 ... 862.8
Unidentified Naphthene 49.41 45.84 ... 863.6
4-Ethylheptane + N 49.65 46.08 ... 865.2
4-Methyloctane 50.10 46.53 ... 868.3
2-Methyloctane 50.26 46.69 ... 869.3
Unidentified Naphthene 50.41 46.84 ... 870.3
Unidentified Naphthene 50.73 47.16 ... 872.5
3-Ethylheptane + N 50.96 47.39 ... 874.0
3-Methyloctane 51.15 47.58 ... 875.3
Unidentified Naphthene 51.35 47.78 ... 876.6
o-Xylene + 1,1,2-Trimethylcyclohexane 51.54 47.97 ... 877.9
Unidentified Naphthene + 2,4,6-Trimethylheptane 51.74 48.17 ... 879.2
Unidentified Naphthene 52.12 48.55 ... 881.8
Unidentified Paraffin 52.24 48.67 ... 882.6
Unidentified Naphthenes 52.56 48.99 ... 884.7
Unidentified Naphthene 52.85 49.28 ... 886.7
Unidentified Naphthene + Paraffin 53.06 49.49 ... 888.1
Unidentified Naphthene 53.26 49.69 ... 889.4
Unidentified Naphthene 53.46 49.89 ... 890.8
Unidentified Naphthene 54.02 50.45 ... 894.5
Unidentified Naphthene 54.40 50.83 ... 897.1
n-Nonane 54.84 51.27 ... 900.0
Unidentified Naphthene 54.98 51.41 ... 900.9
A
Extrapolated from n-C6 and n-C7. See A1.1.3.
B
Extrapolated from n-C8 and n-C9. See A1.2.3.
C
Stereoisomers.

D3700 Practice for Obtaining LPG Samples Using a Float- D6730 Test Method for Determination of Individual Com-
ing Piston Cylinder ponents in Spark Ignition Engine Fuels by 100-Metre
D3710 Test Method for Boiling Range Distribution of Gaso- Capillary (with Precolumn) High-Resolution Gas Chro-
line and Gasoline Fractions by Gas Chromatography matography
(Withdrawn 2014)3 D6733 Test Method for Determination of Individual Com-
D4057 Practice for Manual Sampling of Petroleum and ponents in Spark Ignition Engine Fuels by 50-Metre
Petroleum Products Capillary High Resolution Gas Chromatography
D4175 Terminology Relating to Petroleum Products, Liquid D7096 Test Method for Determination of the Boiling Range
Fuels, and Lubricants Distribution of Gasoline by Wide-Bore Capillary Gas
D5443 Test Method for Paraffin, Naphthene, and Aromatic Chromatography
Hydrocarbon Type Analysis in Petroleum Distillates E355 Practice for Gas Chromatography Terms and Relation-
Through 200 °C by Multi-Dimensional Gas Chromatog- ships
raphy
E594 Practice for Testing Flame Ionization Detectors Used
D6839 Test Method for Hydrocarbon Types, Oxygenated
in Gas or Supercritical Fluid Chromatography
Compounds, Benzene, and Toluene in Spark Ignition
Engine Fuels by Multidimensional Gas Chromatography
3. Terminology
D6729 Test Method for Determination of Individual Com-
ponents in Spark Ignition Engine Fuels by 100 Metre 3.1 Definitions:
Capillary High Resolution Gas Chromatography 3.1.1 This test method makes reference to common gas
chromatographic procedures, terms, and relationships. Detailed
3
The last approved version of this historical standard is referenced on definitions of these can be found in Practices E355 and E594,
www.astm.org. and Terminology D4175.

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4. Summary of Test Method ionization detector designed for optimum response with capil-
4.1 A representative sample of the naphtha is introduced lary columns (with the required gas controls and electronics)
into a gas chromatograph equipped with a methyl silicone must meet or exceed the following specifications:
bonded phase fused silica capillary column. Helium carrier gas Operating temperature 100 °C to 300 °C
Sensitivity >0.015 C/g
transports the vaporized sample through the column in which Minimum detectability 5 × 10−12 g carbon/second
the components are separated. Components are sensed by a Linearity >107
flame ionization detector as they elute from the column. The 7.2 Sample Introduction System—Manual or automatic liq-
detector signal is processed by an electronic data acquisition uid syringe sample injection to the splitting injector may be
system or integrating computer. Each eluting peak is identified employed. Devices capable of 0.2 µL to 1.0 µL injections are
by comparing its retention index to a table of retention indices suitable. It should be noted that inadequate splitter design or
and by visual matching with a standard chromatogram. The poor injection technique, or both, can result in sample frac-
table of retention indices has been established by running tionation. Operating conditions which preclude fractionation
reference compounds under identical conditions or by gas should be determined in accordance with Section 12.
chromatographic—mass spectrometric (GC/MS) analysis of
reference samples under the same conditions, or both. 7.3 Electronic Data Acquisition System—Any data acquisi-
tion and integration device used for quantitation of these
4.2 The mass concentration of each component is deter- analyses must meet or exceed these minimum requirements:
mined by area normalization with response factors. Peaks 7.3.1 Capacity for at least 250 peaks/analysis.
eluting after n-nonane are summed and reported as C10+. 7.3.2 Normalized area percent calculation with response
factors.
5. Significance and Use
7.3.3 Identification of individual components by retention
5.1 A knowledge of the hydrocarbon components compris- time.
ing a petroleum naphtha, reformate, or alkylate is useful in 7.3.4 Noise and spike rejection capability.
valuation of crude oils, in alkylation and reforming process 7.3.5 Sampling rates for fast (<1 s) peaks.
control, in product quality assessment, and for regulatory 7.3.6 Positive and negative sloping baseline correction.
purposes. Detailed hydrocarbon composition is also used as 7.3.7 Peak detection sensitivity for narrow and broad peaks.
input in the mathematical modeling of refinery processes. 7.3.8 Perpendicular drop and tangent skimming as needed.
5.2 Separation of naphtha components by the procedure 7.4 Capillary Column—This test method utilizes a 50 m
described in this test method can result in some peaks that (0.2 mm inside diameter) fused silica capillary column with
represent coeluting compounds. This test method cannot attri- bonded (cross-linked) methyl silicone phase and a film thick-
bute relative concentrations to the coelutants. In the absence of ness (df) of 0.5 µm. Other columns with these nominal
supporting information, use of the results of this test method dimensions may be suitable. However, all columns must meet
for purposes which require such attribution is not recom- the criteria set out in Section 11 for efficiency, resolution, and
mended. polarity.
6. Interferences 8. Reagents and Materials
6.1 If present, olefinic hydrocarbons with boiling points less 8.1 Carrier Gas, helium, mol fraction is 99.99 % pure.
than 150 °C will be separated and detected along with the (Warning—Compressed gas under high pressure.)
saturates and aromatics. Some of the olefins will coelute with
saturates or aromatics and give erroneously high concentra- 8.2 Fuel Gas, hydrogen, mol fraction is 99.9 % pure.
tions for those components. Some coelutions of PNA compo- (Warning—Extremely flammable gas under pressure.)
nents above C7 may occur and results may not be completely 8.3 Make-up Gas, helium or nitrogen, 99.99 % pure.
accurate. Test Method D5443 may be used for carbon number (Warning—Compressed gases under higher pressure.)
distribution above C7 to verify results from this test method. 8.4 n-Heptane, mol fraction is 99+ %. (Warning—
6.2 Alcohols, ethers, and other organic compounds of simi- Flammable. Harmful if inhaled.)
lar volatility can also interfere by coeluting with saturate or 8.5 Methane—(Warning—Extremely flammable gas.)
aromatic hydrocarbons thereby causing erroneously high val-
ues to be determined. 8.6 2-Methylheptane, mol fraction is 99+ %. (Warning—
Flammable. Harmful if inhaled.)
7. Apparatus 8.7 4-Methylheptane, mol fraction is 99+ %. (Warning—
7.1 Instrumentation—A gas chromatograph capable of col- Flammable. Harmful if inhaled.)
umn oven temperature programming from 35 °C to 200 °C in 8.8 2-Methylpentane, mol fraction is 99+ %. (Warning—
1 °C ⁄min increments is required. A heated flash vaporizing Extremely flammable. Harmful if inhaled.)
injector designed to provide a linear sample split injection (for
example, 200:1) is also required for proper sample introduc- 8.9 n-Octane, mol fraction is 99+ %. (Warning—
tion. The associated carrier gas controls must be of adequate Flammable. Harmful if inhaled.)
precision to provide reproducible column flows and split ratios 8.10 Toluene, mol fraction is 99+ %. (Warning—
in order to maintain analytical integrity. A hydrogen flame Flammable. Vapor harmful.)

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8.11 2,3,3-Trimethylpentane, mol fraction is 99+ %. 8.15 Reference Reformate, actual refinery production re-
(Warning—Extremely flammable. Harmful if inhaled.) former product (‘reformate’) for compound identification as in
8.12 Column Evaluation Mixture, a qualitative synthetic Fig. 3. (Warning—Extremely flammable. Harmful if inhaled.)
mixture of pure liquid hydrocarbons with the following ap- NOTE 1—Alkylate, virgin naphtha, and reformer production refinery
proximate composition: 0.5 % toluene, 1 % n-heptane, 1 % reference samples may be available from several vendors; alternatively,
2,3,3-trimethylpentane, 1 % 2-methylheptane, 1 % 4-methyl- in-house production materials or equivalent that matches closely the
heptane, 1 % n-octane in 2-methylpentane solvent. fingerprints in the chromatograms (Figs. 1-3) may be used.
8.13 Reference Alkylate, actual refinery production alky-
lation product used for compound identification as in Fig. 1. 9. Sampling
(Warning—Extremely flammable. Harmful if inhaled.) 9.1 Hydrocarbon liquids (including naphthas) with Reid
8.14 Reference Virgin Naphtha, actual refinery production vapor pressures of 110 kPa (16 psi) or less may be sampled
stream used for compound identification as in Fig. 2. either into a floating piston cylinder or into an open container.
(Warning—Extremely flammable. Harmful if inhaled.) Samples taken into piston samplers may be sampled into a GC

FIG. 1 Reference Alkylate Chromatogram

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FIG. 2 Reference Virgin Naphtha Chromatogram

vial or equivalent provided that upon chilling and transfer does 9.1.2 Open Container Sampling—Refer to Practice D4057
not lead to significant losses of light components. for instructions on manual sampling from bulk storage into
open containers. Stopper container immediately after drawing
NOTE 2—Although possible, this test method has not been evaluated for
sample.
injection of pressurized samples that require high pressure liquid injection
valves. 9.2 Preserve the sample by cooling to approximately 4 °C
9.1.1 Cylinder Sampling—Refer to Test Method D3700 for and by maintaining that temperature until immediately prior to
instructions on transferring a representative sample of a hydro- analysis.
carbon fluid from a source into a floating piston cylinder. Add 9.3 Transfer an aliquot of the cooled sample into a pre-
inert gas to the ballast side of the floating piston cylinder to cooled septum vial, then seal appropriately. Obtain the test
achieve a pressure of 350 kPa (45 psi) above the vapor pressure specimen for analysis directly from the sealed septum vial, for
of the sample. either manual or automatic syringe injection.

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FIG. 3 Reference Reformer Product (Reformate) Chromatogram

10. Preparation of Apparatus 10.2.2 Set the oven temperature to 35 °C and allow oven to
10.1 Install and condition column as per manufacturer’s or equilibrate for at least 15 min, and then observe the tempera-
supplier’s instructions. After conditioning, attach column out- ture reading.
let to flame ionization detector inlet and check for leaks 10.2.3 If the reading of the independent temperature sensor
throughout the system. If leaks are found, tighten or replace is more than 0.5 °C different from 35 °C, follow manufactur-
fittings before proceeding. er’s instructions to adjust calibration of GC oven temperature.
10.2 Calibrate the gas chromatograph column oven tem- NOTE 3—Differences of as little as 1 °C can change the resolution of
perature sensors using an independent, electronic temperature two closely eluting peaks (of dissimilar hydrocarbon types) enough to
measuring device such as a thermocouple or platinum resis- affect integration and quantitation while 2 °C to 3 °C may cause those
same peaks to be unresolved or even reverse their elution order.
tance temperature detector.
10.2.1 Place the independent temperature measuring probe 10.3 Adjust the operating conditions of the gas chromato-
in the oven in the region occupied by the column. Do not allow graph to conform to the list in Table 2. Turn on the detector,
sensor to touch the walls of the oven. ignite flame, and allow the system to equilibrate.

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TABLE 2 Operating Conditions 2 ~ t R~A! 2 t R~B!!
R5 (2)
Column Temperature Program 1.699 ~ W h ~ A ! 1W h ~ B ! !
Initial temperature: 35 °C ± 0.5 °C
Pre-injection equilibration time: 5 min where:
Initial hold time: 30 min
Program rate: 2 °C ⁄min R = resolution,
Final temperature: 200 °C tR(A) = retention time of 4-methylheptane,
Final hold time: 10 min tR(B) = retention time of 2-methylheptane,
Injector
Temperature: 200 °C
Wh(A) = peak width at half-height of 4-methylheptane, and
Split ratio: 200:1 Wh(B) = peak width at half-height of 2-methylheptane
Sample size: 0.2 µL to 1.0 µL
Detector 11.2.3 Determine relative polarity of the column using the
Type: flame ionization difference in Kovats Retention Indices (see Annex A1) of
Temperature: 250 °C toluene and 2,3,3-trimethylpentane. The relative polarity of the
Fuel gas: hydrogen (;30 mL/min)
Oxidizing gas: air (;250 mL/min) column I(2.3,3-TMP)-I(Toluene) must be 0.4 6 0.4 at 35 °C.
Make-up gas: nitrogen (;30 mL/min)
Carrier Gas NOTE 4—This specification is critical. Seemingly slight differences in
Type: helium the polarity have a significant effect on the relative order of elution of
Average linear velocity: ;23 cm/s @35 °C (see 10.4) components, thus making peak identifications difficult.
11.2.3.1 Kovats Retention Index is given by:

10.4 Set carrier gas flow rate such that the retention time of
toluene at 35 °C is 29.6 min 6 0.2 min.
I A 5 7001100 F logt' R ~ A ! 2 logt' R ~ C7 !
logt' R ~ C8 ! 2 logt' R ~ C7 ! G (3)

10.4.1 As a matter of practicality, it may be easier to first set where:

an approximately correct flow rate, using methane gas injec- IA = retention index of component eluting between
tions. To do this, adjust the carrier gas flow (or column head n − C7 and n − C8,
pressure) until the retention time of methane on the 50 m t'R(A) = adjusted retention time of component,
column is 3.6 min. t'R(C7) = adjusted retention time of n-heptane, and
10.4.2 Make final adjustments to flow rate so that toluene is t'R(C8) = adjusted retention time of n-octane.
retained for the specified 29.6 min 6 0.2 min. As this specifi-
11.2.3.2 Adjusted retention time of a peak is determined by
cation is critical to achieving reproducibility of retention times
subtracting the retention time of an unretained substance
among different laboratories, care must be taken that the
(methane) from the retention time of the peak.
toluene does not overload the column and cause skewed peaks
11.2.3.3 If 2,3,3-trimethylpentane and toluene are not
with resultant shifts in peak apex position. Injection of a 1 %
resolved, run separate mixtures, each containing only one of
toluene solution should preclude this possibility.
these compounds along with n-C7 and n-C8 in 2-methylpentane
11. Column Evaluation solvent.
11.1 In order to establish that a column will perform the
12. Split Injection Linearity
required separation, certain specifications must be met with
respect to efficiency, resolution, and polarity. Determine the 12.1 The choice of split ratio used is dependent upon the
following data for new columns. Check older columns on a split linearity characteristics of the particular injector and the
periodic basis to ensure that column deterioration has not sample capacity of the column. Overloading of the column
occurred. A column which does not meet these specifications is may cause loss of resolution for some components and, since
unsuitable for use. overloaded peaks are skewed, variance in retention times. This
can lead to erroneous component identification. During column
11.2 Set oven temperature parameters for isothermal opera-
evaluations and split linearity studies, watch for any skewed
tion. Under isothermal conditions at 35 °C, inject ;25 µL of
peaks that may indicate overload. Note the component size and
methane and record the retention time. Also at 35 °C, analyze
where possible, avoid conditions leading to this problem
the column evaluation mixture described in 8.12. Record the
during actual analyses.
retention times and the peak widths at half height of each of the
components. 12.2 Splitting injector linearity should be established to
11.2.1 Calculate efficiency of the column using Eq 1. The determine proper quantitative parameters and limits. Use a
number of theoretical plates (n) must be greater than 225 000. standard mixture of known mass percentages of 10 to 20 pure
(99 + %) hydrocarbons, covering the boiling range of this test
n 5 5.545 ~ t R /W h ! 2 (1)
method. To prevent losses due to volatility, do not use any
where: compounds lighter than n-pentane.
n = number of theoretical plates, 12.3 Inject and integrate this standard under the following
tR = retention time of n-octane, and conditions, using the operating conditions listed in Table 2.
Wh = peak width of n-octane at half height (in same unit as Split ratio may be determined by direct flow measurements or
retention time). by calculation as shown in Annex A2. Faster temperature
11.2.2 Calculate resolution (R) between 2-methylheptane programming may be used as long as the components are
and 4-methylheptane using Eq 2. R must be at least 1.35. eluted as discrete peaks.

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Injection Temperature: 200 °C. Split: 100:1 Sample: 0.2 µL, 0.5 µL, 1.0 µL due to slight differences in columns, temperature, and flow. As
Split: 200:1 Sample: 0.2 µL, 0.5 µL, 1.0 µL noted in 12.1, retention times and therefore retention indices
Injection Temperature: 250 °C. Split: 100:1 Sample: 0.2 µL, 0.5 µL, 1.0 µL
Split: 200:1 Sample: 0.2 µL, 0.5 µL, 1.0 µL
also vary as a result of column overload.
12.4 Calculate the concentration of each compound in the 14.3 If a computing integrator is used for automatic
mixture by area normalization with response factors. Use a identification, examine the report to ensure peaks are properly
response factor of 1.00 for all compounds except benzene identified.
(0.90) and toluene (0.95). Determine the relative error of the NOTE 7—Careful review of peak identifications is extremely important.
calculated concentrations from the known concentrations. Failure to do so may result in serious errors.
% relative error (4) 14.4 Sum the areas of all peaks eluting after n-nonane. This
group will be treated as a single component, C10+.
100 3 ~ calculated concentration 2 known concentration!
5
known concentration 14.5 Calculate the mass percent of each component (includ-
ing C10+) according to the following equation:
12.5 Use only those combinations of conditions from 12.3
which result in 3 % or less relative error. This is the splitter Ai 3 Bi
Mass % component i 5 3 100 (5)
linearity range. ( ~A i 3 B i!

13. Procedure for Gas Chromatographic Analysis of where:

Sample Ai = area of peak representing component i, and
Bi = relative mass response factor for component i. Use a
13.1 Set the instrument operating variables to within the response factor of 1.00 for all components except
limits specified in Table 2. If necessary, change split ratio, benzene (0.90) and toluene (0.95).
sample size, or injection port temperature, or combination NOTE 8—Relative mass response factors determined using quantitative
thereof, to ensure splitter linearity as determined in Section 12. calibration standards may be substituted for the assigned factors in 14.5.
However, the reproducibility of the test method (Table 3) is based on data
13.2 Verify that the isothermal retention time of toluene (at calculated using the assigned factors. Differences in interlaboratory results
35 °C) is 29.6 min 6 0.2 min as discussed in 10.4. on the same sample may exceed the published reproducibility values as a
13.3 Set the recorder or integration device, or both, for result of using empirically determined response factors.
accurate presentation of the data. Set up instrument sensitivity 15. Report
such that any component of at least 0.05 % mass will be
detected, integrated, and reported. 15.1 Report the mass percent and identity of each compo-
nent through n-nonane to the nearest 0.01 %.
13.4 Inject 0.2 µL to 1.0 µL of sample into the injection port
and start the analysis. Sample size must be consistent with the 15.2 Report the mass percent of C10+ to the nearest 0.01 %.
splitter linearity range as determined in Section 12. Obtain a 15.3 Report the total mass percent of all unidentified com-
chromatogram and peak integration report. ponents through n-nonane.
NOTE 5—Petroleum naphtha samples may contain appreciable quanti-
ties of highly volatile components. Samples should be chilled in their TABLE 3 Repeatability and Reproducibility for Selected Naphtha
original container to 4 °C (39 °F) before opening for subsampling or Components
transfer (see Section 9).
Component Name Repeatability Reproducibility
Isobutane 0.071(x)0.85 0.13(x)0.85
14. Calculation n-Butane 0.091(x)0.85 0.17(x)0.85
Isopentane 0.072(x)0.67 0.17(x)0.67
14.1 Identify each peak by visually matching it with its n-Pentane 0.051(x)0.67 0.14(x)0.67
counterpart in the appropriate standard chromatogram, Fig. 1, CyclopentaneA 0.026(x)0.50 0.087(x)0.50
Fig. 2, or Fig. 3. Make allowances for differences in relative 2,3-DimethylbutaneA 0.027(x)0.67 0.12(x)0.67
3-Methylpentane 0.015(x) 0.034(x)
peak sizes with different samples. Peaks eluting after n-nonane Methylcyclopentane 0.016(x) 0.038(x)
are not identified individually. Benzene 0.037(x)0.67 0.092(x)0.67
2,3-DimethylpentaneA 0.014(x) 0.051(x)
NOTE 6—To aid the analyst in setting up this test method and 3-EthylPentaneA 0.019(x) 0.094(x)
identifying peaks in the chromatograms, qualitative reference samples of n-Heptane 0.012(x)0.50 0.030(x)0.50
the alkylate, virgin naphtha, and reformate actually used to generate Fig. trans-1,2-DimethylcyclopentaneA 0.016(x) 0.053(x)
1, Fig. 2, and Fig. 3 are available. Each can be analyzed and its Methylcyclohexane 0.065(x)0.50 0.16(x)0.50
chromatogram compared directly with the corresponding figure to assist in Toluene 0.015(x) 0.031(x)
peak assignments. 2,5-Dimethylhexane 0.012(x) 0.030(x)
2-Methylheptane 0.037(x)0.50 0.094(x)0.50
14.2 Each peak can also be identified by matching its n-Octane 0.010(x) 0.070(x)
trans-1,2-Dimethylcyclohexane 0.010(x) 0.024(x)
retention index with that of the compounds listed in Table 1.
1,1-Dimethylcyclohexane 0.0095 % 0.023 %
Equations for calculating retention indices are given in Annex p-XyleneA 0.018(x) 0.15(x)
A1. Retention indices of compounds eluted during the initial 2,2-Dimethylheptane 0.0050 % 0.0099 %
4-MethyloctaneA 0.029(x)0.50 0.073(x)0.50
isothermal portion of the analysis must be calculated using the n-NonaneA 0.017(x) 0.050(x)
Kovats equation. Retention indices of all other components A
Component that is incompletely resolved, (x) refers to the mass percent
must be calculated using the equation for linear indices. component found.
Differences from the values in the table must be allowed for

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 D5134 − 21
16. Precision and Bias4 operation of the test method, exceed the repeatability values
16.1 Precision—The precision of any individual measure- shown in Table 3 only in one case in twenty.
ment resulting from the application of this test method depends 16.1.2 Reproducibility—The difference between two single
on several factors including the volatility of the component, its and independent test results obtained by different operators
concentration, and the degree to which it is resolved from other working in different laboratories on identical test materials
closely eluting components. As it is not practical to determine would, in the long run, in the normal and correct operation of
the precision of measurement for every component (or group of the test method, exceed the values shown in Table 3 only in one
components) separated by this test method, Table 3 presents case in twenty.
the repeatability and reproducibility values for selected, repre- 16.2 Bias—Bias in the measurements resulting from the
sentative components. application of this test method cannot be determined since
16.1.1 Repeatability—The difference between successive there is no accepted reference material suitable for determining
test results obtained by the same operator with the same bias.
apparatus under constant operating conditions on identical test
materials would, in the long run, in the normal and correct 17. Keywords
17.1 alkylate; aromatics; capillary gas chromatography; de-
4
Supporting data have been filed at ASTM International Headquarters and may
tailed hydrocarbon analysis; DHA; hydrocarbon composition;
be obtained by requesting Research Report RR:D02-1265. Contact ASTM Customer naphtha; naphthenes; paraffin; petroleum naphtha; PNA; refor-
Service at [email protected]. mate; virgin naphtha

ANNEXES

(Mandatory Information)

A1. KOVATS AND LINEAR RETENTION INDICES

A1.1 The logarithmic Kovats Retention Index5 is a gas A1.1.4 By definition the Kovats Retention Indices of
chromatographic parameter characteristic of a solute’s relative n-alkanes are 100 × N (for example, for n-hexane, I = 600 and
retention on a specified liquid phase at a specified (isothermal) for n-heptane, I = 700).
temperature. It is a very useful tool in the qualitative identifi- A1.1.5 Kovats Retention Indices are calculated from ad-
cation of chromatographic peaks. justed retention times obtained from a strictly isothermal
A1.1.1 Based on the observation that under isothermal analysis or from the initial isothermal temperature hold portion
conditions the adjusted retention times of members of a (if used) of a programmed temperature analysis. One may not
homologous series increase logarithmically with increasing utilize data from isothermal portions of an analysis which
carbon number, the Kovats Retention Index is a number follow temperature changes incurred during a run.
indicating (on a logarithmic scale) the retention of a compound A1.1.6 These indices are independent of other operating
relative to the series of n-alkanes. (Adjusted retention time is parameters. Kovats Retention Indices calculated from retention
the actual retention time minus the retention time of an times determined on any suitable chromatographic system can
unretained component such as methane.) be compared directly with those from any other suitable system
A1.1.2 The equation used to calculate the Kovats Retention as long as the liquid phase and the temperature are the same.
Index Iiso of a compound A is given by Eq A1.1: Published compilations are an excellent source of indices for
identification purposes.
I iso 5 100 3 N1100 3 S logt' R ~ A ! 2 logt' R ~ N !
logt' R ~ N11 ! 2 logt' R ~ N ! D (A1.1)
A1.2 The Linear Retention Index6 is an extension of the
where t'R(N) and t'R(N + 1) are the adjusted retention times of Kovats concept to programmed temperature gas chromatogra-
n-alkanes of carbon number N and N + 1 that are respectively phy. The Linear Retention Index of a solute is dependent not
smaller and larger than t'R(A), the adjusted retention time of a only on the liquid phase but on other operating parameters as
compound A. well. It is a useful indicator of relative retention of solutes on
chromatographic systems operating under identical or nearly
A1.1.3 Over a limited range and with some loss in accuracy, identical conditions.
Kovats Retention Indices can be calculated by extrapolation
rather than interpolation. In such case N and N + 1 would be A1.2.1 Based on the approximation that under programmed
defined as the carbon numbers of consecutive n-alkanes, both temperature conditions the actual retention times of members
eluting immediately before (or after) compound A. The equa- of a homologous series increase linearly with increasing carbon
tion otherwise remains unchanged.

5 6
Kovats, E., Advances in Chromatography, Vol 1, 1964. Van den Dool and Dratz, Journal of Chromatography, Vol 11, 1963, p. 463.

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 D5134 − 21
number, the Linear Retention Index is a number indicating (on eluting immediately after (or before) compound A. The equa-
a linear scale) the retention of a compound relative to the series tion otherwise remains unchanged.
of n-alkanes. A1.2.4 By definition, the Linear Retention Indices of
A1.2.2 The equation used to calculate the Linear Retention n-alkanes are 100 × N (for example, for n-octane, I = 800 and
Index (Iprog) of a compound A is given by Eq A1.2: for n-nonane, I = 900).
A1.2.5 The usual application of the Linear Retention Index
I prog 5 100 3 N1100 3 S t R~A! 2 t R~N!
t R ~ N11 ! 2 t R ~ N ! D (A1.2) system is to linear programmed temperature analyses without
isothermal plateaus (even at the beginning of the run).
where tR is the actual retention time and the subscripts, A, N, However, since the indices are generally limited to analyses
and N + 1 are defined as in A1.1.2 above. with essentially identical operating conditions anyway, some
analysts have used the Linear Retention Index system to reduce
A1.2.3 Over a limited range and with some loss in accuracy, data from procedures utilizing complex temperature profiles.
Linear Retention Indices can be calculated by extrapolation Such indices are not theoretically defensible, but nevertheless
rather than interpolation. In such cases, N and N + 1 would be are useful indicators of relative retention especially for stan-
defined as the carbon numbers of consecutive n-alkanes, both dard test methods.

A2. MEASUREMENT AND CALCULATION OF FLOW PARAMETERS

A2.1 Column flow rate can be measured directly on some A2.2.6 Column Carrier Gas Flow Rate (cm3/min):
instruments at the flame ionization detector jet using a soap F c 5 µ o 3 A c 3 60 (A2.6)
film flow-meter. This is the preferred way as long as all other
gas flows can be turned off during the measurement. A2.3 Injection Split Ratio:
A2.2 Column flow rate can also be calculated from column F c 1F v
Split ratio 5 (A2.7)
dimensions and flow parameters using the following series of Fc
equations: where Fv is the directly measured flow rate through the
splitter vent.
A2.2.1 Column Hold-up Time (s):
t m 5 retention time of methane (A2.1) A2.4 Example—Given a 50 m column of 0.21 mm inside
diameter, inlet pressure of 220 kPa (gage), outlet pressure of
A2.2.2 Average Linear Gas Velocity (cm/s):
101 kPa (absolute), retention time of methane of 3.62 min, and
µ̄ 5 L/t m (A2.2) flow out the splitter vent of 200 cm3/min, calculate column
when L is the column length, cm. flow rate and split ratio as follows:

A2.2.3 Gas Compressibility Correction Factor: t m 5 3.62min 5 217 s (A2.8)

3 ~p2 2 1! µ̄ 5 ~ 5000! / ~ 217! 5 23.0 cm/s

j5 3 (A2.3)
2 ~p3 2 1!
~ 220 kPa1101 kPa!
where p is the ratio of column inlet to column outlet absolute P5 5 3.18
101 kPa
pressure.
j 5 3/2 3 @ ~ 3.18 2 2 1 ! / ~ 3.18 3 2 1 ! # 5 0.438
A2.2.4 Column Outlet Linear Velocity (cm/s):
µ o 5 µ̄/j (A2.4) µ o 5 23.0/0.438 5 52.5 cm/s
2
A2.2.5 Column Cross-Sectional Area (cm ): π 3 ~ 0.021! 2
Ac 5 5 0.000346 cm2
π ~ d i! 2 4
Ac 5 (A2.5)
4
F c 5 52.5 3 0.000346 3 60 5 1.09 cm 3 /min
where di is the internal diameter of the column, cm. Split ratio = (200 + 1.09)/1.09 = 184:1

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SUMMARY OF CHANGES

Subcommittee D02.04 has identified the location of selected changes to this standard since the last issue
(D5134 – 13 (2017)) that may impact the use of this standard. (Approved Dec. 1, 2021.)

(1) Added Practices E355 and E594, and Terminology D4175 (2) Added Section 3.
to Section 2.

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