An American National Standard

Designation: D 5580 – 02

Standard Test Method for

Determination of Benzene, Toluene, Ethylbenzene, p/m-
Xylene, o-Xylene, C9 and Heavier Aromatics, and Total
Aromatics in Finished Gasoline by Gas Chromatography1
This standard is issued under the fixed designation D 5580; 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 (e) indicates an editorial change since the last revision or reapproval.

1. Scope priate safety and health practices and determine the applica-
1.1 This test method covers the determination of benzene, bility of regulatory limitations prior to use.
toluene, ethylbenzene, the xylenes, C9 and heavier aromatics, 2. Referenced Documents
and total aromatics in finished motor gasoline by gas chroma-
tography. 2.1 ASTM Standards:
1.2 The aromatic hydrocarbons are separated without inter- D 1298 Test Method for Density, Relative Density, (Specific
ferences from other hydrocarbons in finished gasoline. Non- Gravity) or API Gravity of Crude Petroleum and Liquid
aromatic hydrocarbons having a boiling point greater than Petroleum Products by Hydrometer Method2
n-dodecane may cause interferences with the determination of D 4052 Test Method for Density and Relative Density of
the C9 and heavier aromatics. For the C8 aromatics, p-xylene Liquids by Digital Density Meter3
and m-xylene co-elute while ethylbenzene and o-xylene are D 4057 Practice for Manual Sampling of Petroleum and
separated. The C9 and heavier aromatics are determined as a Petroleum Products3
single group. D 4307 Practice for Preparation of Liquid Blends for Use as
1.3 This test method covers the following concentration Analytical Standards3
ranges, in liquid volume %, for the preceding aromatics: E 355 Practice for Gas Chromatography Terms and Rela-
benzene, 0.1 to 5 %; toluene, 1 to 15 %; individual C8 tionships4
aromatics, 0.5 to 10 %; total C9 and heavier aromatics, 5 to 3. Terminology
30 %, and total aromatics, 10 to 80 %.
1.4 Results are reported to the nearest 0.01 % by either mass 3.1 Definitions of Terms Specific to This Standard:
or by liquid volume. 3.1.1 aromatic—any organic compound containing a ben-
1.5 Many of the common alcohols and ethers that are added zene ring.
to gasoline to reduce carbon monoxide emissions and increase 3.1.2 low-volume connector—a special union for connect-
octane, do not interfere with the analysis. Ethers such as methyl ing two lengths of narrow bore tubing 1.6-mm (0.06-in.)
tert-butylether (MTBE), ethyl tert-butylether (ETBE), tert- outside diameter and smaller; sometimes this is referred to as
amylmethylether (TAME), and diisopropylether (DIPE) have zero dead volume union.
been found to elute from the precolumn with the nonaromatic 3.1.3 narrow bore tubing—tubing used to transfer compo-
hydrocarbons to vent. Other oxygenates, including methanol nents prior to or after separation; usually 0.5-mm (0.02-in.)
and ethanol elute before benzene and the aromatic hydrocar- inside diameter and smaller.
bons. 1-Methylcyclopentene has also been found to elute from 3.1.4 split ratio—in capillary gas chromatography, the ratio
the precolumn to vent and does not interfere with benzene. of the total flow of carrier gas to the sample inlet versus the
1.6 The values stated in SI units are to be regarded as flow of the carrier gas to the capillary column, expressed by:
standard. The values given in parentheses are provided for split ratio 5 ~S 1 C!/C (1)
information only; they may not be exact equivalents.
1.7 This standard does not purport to address all of the where:
S = flow rate at the splitter vent and
safety concerns, if any, associated with its use. It is the
C = flow rate at the column outlet.
responsibility of the user of this standard to establish appro-
3.1.5 1,2,3-tris-2-cyanoethoxypropane (TCEP)—a polar gas
chromatographic liquid phase.
1
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
2
D02.04.0L on Gas Chromatography. Annual Book of ASTM Standards, Vol 05.01.
3
Current edition approved Jan. 10, 2002. Published March 2002. Originally Annual Book of ASTM Standards, Vol 05.02.
4
published as D 5580 – 94. Last previous edition D 5580 – 00. Annual Book of ASTM Standards, Vol 14.02.

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

1
 D 5580
3.1.6 wall-coated open tubular (WCOT)—a type of capil- 4.4 The flame ionization detector response, proportional to
lary column prepared by coating the inside wall of the capillary the concentration of each component, is used to calculate the
with a thin film of stationary phase. amount of aromatics that are present with reference to the
internal standard.
4. Summary of Test Method
4.1 A two-column chromatographic system equipped with a 5. Significance and Use
column switching valve and a flame ionization detector is used. 5.1 Regulations limiting the concentration of benzene and
A reproducible volume of sample containing an appropriate the total aromatic content of finished gasoline have been
internal standard such as 2-hexanone is injected onto a precol- established for 1995 and beyond in order to reduce the ozone
umn containing a polar liquid phase (TCEP). The C9 and reactivity and toxicity of automotive evaporative and exhaust
lighter nonaromatics are vented to the atmosphere as they elute emissions. Test methods to determine benzene and the aromatic
from the precolumn. A thermal conductivity detector may be content of gasoline are necessary to assess product quality and
used to monitor this separation. The TCEP precolumn is to meet new fuel regulations.
backflushed immediately before the elution of benzene, and the 5.2 This test method can be used for gasolines that contain
remaining portion of the sample is directed onto a second oxygenates (alcohols and ethers) as additives. It has been
column containing a nonpolar liquid phase (WCOT). Benzene, determined that the common oxygenates found in finished
toluene, and the internal standard elute in the order of their gasoline do not interfere with the analysis of benzene and other
boiling points and are detected by a flame ionization detector. aromatics by this test method.
Immediately after the elution of the internal standard, the flow
through the nonpolar WCOT column is reversed to backflush 6. Apparatus
the remainder of the sample (C8 and heavier aromatics plus C10
and heavier nonaromatics) from the column to the flame 6.1 Chromatographic System—See Practice E 355 for spe-
ionization detector. cific designations and definitions. Refer to Fig. 1 for a diagram
4.2 The analysis is repeated a second time allowing the C12 of the system.
and lighter nonaromatics, benzene and toluene to elute from 6.1.1 Gas Chromatograph (GC), capable of operating at the
the polar TCEP precolumn to vent. A thermal conductivity conditions given in Table 1, and having a column switching
detector may be used to monitor this separation. The TCEP and backflushing system equivalent to Fig. 1. Carrier gas
precolumn is backflushed immediately prior to the elution of pressure and flow control devices shall be capable of precise
ethylbenzene and the remaining aromatic portion is directed control when column head pressures and flow rates are low.
into the WCOT column. The internal standard and C8 aromatic 6.1.2 Sample Introduction System, capable of introducing a
components elute in the order of their boiling points and are representative sample into the gas chromatographic inlet.
detected by a flame ionization detector. Immediately after Microlitre syringes and automatic syringe injectors have been
o-xylene has eluted, the flow through the nonpolar WCOT used successfully.
column is reversed to backflush the C9 and heavier aromatics to 6.1.3 Inlet System, (splitting type)— Split injection is nec-
the flame ionization detector. essary to maintain the actual chromatographed sample size
4.3 From the first analysis, the peak areas of benzene, within the limits required for optimum column efficiency and
toluene, and the internal standard (2-hexanone) are measured detector linearity.
and recorded. Peak areas for ethylbenzene, p/m-xylene, 6.1.3.1 Some gas chromatographs are equipped with on-
o-xylene, the C9 and heavier aromatics, and internal standard column injectors and autosamplers which can inject submi-
are measured and recorded from the second analysis. The crolitre sample sizes. Such systems can be used provided that
backflush peak eluting from the WCOT column in the second column efficiency and detector linearity are comparable to
analysis contains only C9 and heavier aromatics. systems with split injection.

FIG. 1 Valve Diagram, Aromatics in Gasoline

2
 D 5580
TABLE 1 Typical Chromatographic Operating Parameters 130 be able to calculate the correlation coefficient (r2) and linear
Temperatures least square fit equation for each calibration data set in
Injection port (split injector) 200°C accordance with 11.4.
FID (Detector A) 250°C 6.3 Chromatographic Columns (two columns are used):
TCD (Detector B) 200°C
Nonpolar WCOT capillary
6.3.1 Polar Precolumn, to perform a pre-separation of the
Initial 60°C (6 min) aromatics from nonaromatic hydrocarbons in the same boiling
Program rate 2°C/min point range. Any column with equivalent or better chromato-
Final 115°C (hold until all
components elute)
graphic efficiency and selectivity in accordance with 6.3.1.1
Polar TCEP precolumn (temperature to 60°C or same as nonpolar WCOT can be used.
remain constant before time to capillary if TCEP/WCOT columns 6.3.1.1 TCEP Micro-Packed Column, 560-mm (22-in.) by
BACKFLUSH, T1 or T2. Do not exceed contained in identical heated zone.
maximum operating temperature.)
1.6-mm (1⁄16-in.) outside diameter by 0.76-mm (0.030-in.)
Valve >115°C or same as nonpolar WCOT inside diameter stainless steel tube packed with 0.14 to 0.15 g
capillary if valve and WCOT column of 20 % (mass/mass) TCEP on 80/100 mesh Chromosorb
contained in identical heated zone.
P(AW). This column was used in the cooperative study to
Flows and Conditions
provide the precision and bias data referred to in Section 15.
Carrier gas helium 6.3.2 Nonpolar (Analytical) Column—Any column with
Flow to TCEP precolumn (split injector) 10 mL/min
Flow to WCOT capillary (auxiliary flow) 10 mL/min
equivalent or better chromatographic efficiency and selectivity
Flow from split vent 100 mL/min in accordance with 6.3.2.1 can be used.
Detector gases as necessary 6.3.2.1 WCOT Methyl Silicone Column, 30 m long by
Split ratio 11:1
Sample size 1 µL 0.53-mm inside diameter fused silica WCOT column with a
5.0-µm film thickness of cross-linked methyl siloxane.

6.1.4 Detector—A flame ionization detector (Detector A) is 7. Reagents and Materials

employed for quantitation of components eluting from the 7.1 Carrier Gas, appropriate to the type of detector used.
WCOT column. The flame ionization detector used for Detec- Helium has been used successfully. The minimum purity of the
tor A shall have sufficient sensitivity and stability to detect 0.01 carrier gas used must be 99.95 mol %. Additional purification
volume % of an aromatic compound. may be necessary to remove trace amounts of oxygen.
6.1.4.1 It is strongly recommended that a thermal conduc- (Warning—Helium is usually supplied as a compressed gas
tivity detector be placed on the vent of the TCEP precolumn under high pressure.)
(Detector B). This facilitates the determination of valve 7.2 Methylene Chloride—Used for column preparation. Re-
BACKFLUSH and RESET times (10.5) and is useful for agent grade, free of nonvolatile residue. (Warning—Harmful
monitoring the separation of the polar TCEP precolumn. when ingested or inhaled at high concentrations.)
6.1.5 Switching and Backflushing Valve, to be located within 7.3 2,2,4-Trimethylpentane (isooctane)— Used as a solvent
a temperature-controlled heated zone and capable of perform- in the preparation of the calibration mixture. Reagent grade.
ing the functions in accordance with Section 10, and illustrated (Warning—Isooctane is flammable and can be harmful or fatal
in Fig. 1. The valve shall be of low internalvolume design and when ingested or inhaled.
not contribute significantly to deterioration of chromatographic 7.4 Standards for Calibration and Identification, required
resolution. for all components to be analyzed and the internal standard.
6.1.5.1 A 10-port valve with 1.6-mm (0.06) outside diam- Standards are used for establishing identification by retention
eter fittings is recommended for this test method. Alternately, time as well as calibration for quantitative measurements.
and if using columns of 0.32-mm inside diameter or smaller, a These materials shall be of known purity and free of the other
valve with 0.8-mm (0.03-in.) outside diameter fittings should components to be analyzed. (Warning—These materials are
be used. flammable and may be harmful or fatal when ingested or
6.1.5.2 Some gas chromatographs are equipped with an inhaled.
auxiliary oven which can be used to contain the valve. In such
a configuration, the valve can be kept at a higher temperature 8. Preparation of Columns
than the polar and nonpolar columns to prevent sample 8.1 TCEP Column Packing:
condensation and peak broadening. The columns are then 8.1.1 Use any satisfactory method, that will produce a
located in the main oven and the temperature can be adjusted column capable of retaining aromatics from nonaromatic
for optimum aromatic resolution. components of the same boiling point range in a gasoline
6.1.5.3 An automatic valve switching device is strongly sample. The following procedure has been used successfully.
recommended to ensure repeatable switching times. 8.1.2 Completely dissolve 10 g of TCEP in 100 mL of
6.2 Data Acquisition System: methylene chloride. Next add 40 g of 80/100 mesh Chro-
6.2.1 Integrator or Computer, capable of providing real- mosorb P(AW) to the TCEP solution. Quickly transfer this
time graphic and digital presentation of the chromatographic mixture to a drying dish, in a fume hood, without scraping any
data are recommended for use. Peak areas and retention times of the residual packing from the sides of the container.
can be measured by computer or electronic integration. Constantly, but gently, stir the packing until all of the solvent
6.2.1.1 It is recommended that this device be capable of has evaporated. This column packing can be used immediately
performing multilevel internal-standard-type calibrations and to prepare the TCEP column.

3
 D 5580
8.2 Micro-packed TCEP Column: 10.3.2 Attach a flow measuring device to the split injector
8.2.1 Wash a straight 560-mm (22-in.) length of 1.6-mm vent and adjust the flow from the split vent using the flow
(1⁄16-in.) outside diameter, 0.76-mm (0.030-in.) inside diameter controller to provide a flow of 100 mL/min. Recheck the
stainless steel tubing with methanol and dry with compressed column vent flow set in 10.3.1 and adjust, if necessary. The
nitrogen. split ratio should be approximately 11:1.
8.2.2 Insert 6 to 12 strands of silvered wire, a small mesh 10.3.3 Switch the valve to BACKFLUSH position and
screen or stainless steel frit inside one end of the tube. Slowly adjust the variable restrictor to give the same precolumn vent
add 0.14 to 0.15 g of packing material to the column and gently flow set in 10.3.1. This is necessary to minimize flow changes
vibrate to settle the packing inside the column. Insert silvered when the valve is switched.
wire, mesh screen, or frit to the other end of the tube to prevent 10.3.4 Switch the valve to the RESET position and adjust
the packing material from falling. When strands of wire are the auxiliary flow controller to give a flow of 10 mL/min at the
used to retain the packing material inside the column, leave 6.0 Detector A (FID) exit.
mm (0.25 in.) of space at the top of the column. 10.4 Detector Setup—Depending on the particular type of
8.3 WCOT Methyl Silicone Column—It is suggested that instrumentation used, adjust the hydrogen, air, and makeup
this column be purchased directly from a suitable capillary flows to the flame ionization detector and ignite the flame. If a
column manufacturer (see 6.3.2.1). thermal conductivity detector (Detector B) is being used to
monitor the vent effluent in the valve RESET position, set the
9. Sampling reference flow and turn on the detector circuit.
9.1 Every effort should be made to ensure that the sample is 10.5 Valve Backflush and Reset Times:
representative of the fuel source from which it is taken. Follow 10.5.1 The time to BACKFLUSH and RESET the valve will
the recommendations of Practice D 4057, or its equivalent, vary slightly for each column system and must be determined
when obtaining samples from bulk storage or pipelines. as described in 10.5.1.1, 10.5.1.2, and 10.5.1.3. The start time
9.2 Appropriate steps should be taken to minimize the loss of the integrator or computer system and valve timer must be
of light hydrocarbons from the gasoline sample to be analyzed. synchronized with the injection to accurately reproduce the
Upon receipt in the laboratory, chill the sample in its original backflush time. This procedure assumes that a thermal conduc-
container from 0 to 5°C (32 to 40°F) before and after tivity detector is installed on the precolumn vent line as
sub-sampling is performed. Detector B (see 6.1.4.1). If a detector is not available, the
9.3 If necessary, transfer the chilled sample to a vaportight appropriate valve BACKFLUSH times, T1 and T2, must be
container and store at 0 to 5°C (32 to 40°F) until needed for determined experimentally. If the BACKFLUSH times, T1 and
analysis. T2, are not set correctly (switched too late), it is possible that
part of the benzene and ethylbenzene peaks will be vented.
10. Preparation of Apparatus and Establishment of 10.5.1.1 Adjust the valve to RESET (forward flow) and
Conditions inject 1.0 µL of a blend containing approximately 5 % each of
benzene, ethylbenzene, o-xylene, and 2-hexanone in isooctane.
10.1 Assembly—Connect the TCEP and WCOT column to
This mixture is used to set the valve timing, therefore, the exact
the valve system (Fig. 1) using low-volume connectors and
concentration need not be known. Alternatively, the calibration
narrow bore tubing. It is important to minimize the volume of
mixture can be used for this test. Determine retention time in
the chromatographic system that comes in contact with the
seconds at which benzene and ethylbenzene start to elute as
sample, otherwise peak broadening will occur.
measured by Detector B. Subtract 6 s from each of these and
10.2 Initial Operating Conditions—Adjust the operating
call these times to BACKFLUSH, T1 and T2, respectively. The
conditions to those listed in Table 1, but do not turn on the
correct time for T1 and T2 is just prior to the elution of benzene
detector circuits. Check the system for leaks before proceeding
and ethylbenzene from the TCEP precolumn.
further.
10.2.1 If different polar and nonpolar columns are used, or NOTE 1—Fig. 2 is an example chromatogram illustrating the elution of
WCOT capillary columns of smaller inner diameter or different a calibration mixture from the polar precolumn using the procedure
film thickness, or both, are used, it may be necessary to use described in 10.5.1.1. Times to BACKFLUSH, T1 and T2, are indicated
on the chromatogram. The times to BACKFLUSH, T1 and T2, should be
different optimum flows and temperatures.
optimized for each chromatographic system.
10.2.2 Conditions listed in Table 1 are applicable to the
columns described in 6.3. If a WCOT column of a different film 10.5.1.2 Reinject the calibration blend and turn the valve to
thickness is used, the conditions chosen for the analysis must BACKFLUSH at time T1. When the internal standard peak
sufficiently separate toluene from the internal standard (first (2-hexanone) returns to baseline switch valve back to RESET
analysis) and ethylbenzene from the xylenes (second analysis). (forward flow) position. Call this time T3.
10.3 Flow Rate (Carrier Gas) Adjustments: 10.5.1.3 Reinject the calibration blend and BACKFLUSH at
10.3.1 Attach a flow measuring device to the precolumn time T2. When the o-xylene peak returns to baseline, switch
vent (or Detector B) with the valve in the RESET or forward the valve back to RESET (forward flow). Call this time T4.
flow position and adjust the pressure of the capillary injection 10.6 Polar Precolumn Selectivity Check:
port (Fig. 1) to give 10.0-mL/min flow (17 to 20 psi). Soap 10.6.1 The selectivity of the polar precolumn is critical to
bubble flow meters are suitable. This represents the flow allow for accurate determination of the C9 and heavier aromat-
through the polar precolumn. ics without non-aromatic interferences. The selectivity must be

4
 D 5580

FIG. 2 Determination of Precolumn Backflush Times, T1 and T2

verified so that for the second analysis, when the time to 11. Calibration
BACKFLUSH T2 is properly adjusted, all of the C12 and 11.1 Preparation of Calibration Samples— Prepare multi-
lighter nonaromatic hydrocarbons are vented from the polar component calibration standards of benzene, toluene, ethylben-
precolumn while the heavier aromatics are retained. The zene, o-xylene, and 1,2,4-trimethylbenzene at concentrations
following test can be used to verify the precolumn perfor- of interest by mass in accordance with Practice D 4307.
mance. O-xylene is used to represent the xylenes while 1,2,4-
10.6.1.1 Prepare a blend containing approximately 1.5 % trimethylbenzene is used for the C9 and heavier aromatics. For
n-dodecane in 2,2,4-trimethylpentane (isooctane). n-Dodecane each aromatic component, use at least five calibration points
is used to represent the high boiling nonaromatic hydrocarbons and ensure that the concentration of each aromatic component
in gasoline. Inject 1.0 µL of the mixture under the conditions is within its calibration range. For benzene, calibration con-
specified in 10.2 to 10.5 and actuate the valve at time T2 centrations of 0.1, 0.5, 1.0, 2.0, and 5 volume percent can be
(BACKFLUSH) and time T4 (RESET). Record the signals used. For toluene: 1.0, 2.5, 5.0, 10.0, and 15.0 volume %. For
from both the flame ionization (Detector A) and thermal ethylbenzene, o-xylene, and 1,2,4-trimethylbenzene: 0.5, 1.0,
conductivity (Detector B) detectors. Verify that n-dodecane 2.5, 5.0, and 10 volume % can be used. The relative densities
listed in Table 2 shall be used as a guide in determining the
fully elutes from the polar precolumn before BACKFLUSH
proper mass of aromatic components that need to be added in
time T2. When monitoring the thermal conductivity detector
order to arrive at a target volume percent concentration.
(Detector B), the n-dodecane peak should return to baseline
11.2 Before preparing the standards, determine the purity of
before BACKFLUSH time T2. If not, part of the n-dodecane the aromatics by capillary GC and make corrections for the
peak will be backflushed to the non-polar WCOT column and impurities found. Whenever possible, use stocks of at least
be detected by the flame ionization detector after the valve 99.9 % purity.
RESET time T4. If a thermal conductivity detector is not
available on the precolumn vent line, the chromatogram TABLE 2 Physical Constants
obtained by the flame ionization detector can be used to verify Relative Density
that all the n-dodecane is being vented. This chromatogram Component
(15.56/15.56°C)A
should not show any significant response from n-dodecane Benzene 0.8845
after the RESET time T4. Toluene 0.8719
Ethylbenzene 0.8717
10.6.1.2 If all of the n-dodecane peak is not completely p/m-Xylene 0.8679
vented from the polar precolumn, as measured by the thermal o-Xylene 0.8848
1,2,4-Trimethylbenzene 0.8806
conductivity or flame ionization detector, recheck instrument C9 plus aromatics 0.8764
parameters and valve backflush times (10.5) or replace the 2-hexanone 0.8162
polar precolumn. If the valve is contained in a separate A
“Physical Constants of Hydrocarbons C 1–C10,” STP 109A, ASTM Interna-
isothermal heated zone, it may be necessary to use a higher tional, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA
19428–2959. The mixed xylene (p/m-xylene) density based upon a 1:3 ratio of
temperature to prevent absorption of small amounts of p-xylene to m-xylene. C9 plus aromatics based upon the average relative density
n-dodecane on the rotor or transfer tubing surfaces. values of the 30 C9-C10 aromatics.

5
 D 5580
11.3 Prepare standards by transferring a fixed volume of
aromatic component using pipettes, eye droppers, or syringes
to 100-mL volumetric flasks or 100-mL septum-capped vials as
follows. Cap and record the tare weight of the volumetric flask
or vial to 0.1 mg. Remove the cap and carefully add the
aromatic components to the flask or vial starting with the least
volatile (1,2,4-trimethylbenzene). Cap the flask and record the
net mass (Wi) of the aromatic component added to 0.1 mg.
Repeat the addition and weighing procedure for each aromatic
component. Do not exceed 50 volume % for all aromatics
added. Similarly, add 10 mL of the internal standard,
2-hexanone, and record its net mass ( Ws) to 0.1 mg. Dilute
each standard to the mark with aromatics free 2,2,4-
trimethylpentane (isooctane). Store the capped calibration
standards in a refrigerator at 0 to 5°C (32 to 40°F) when not in
use.
11.4 Calibration Procedure—With the valve initially in the
RESET mode, chromatograph each of the calibration mixtures
(11.1) twice using valve timing procedures in accordance with
10.5. For the first analysis use times T1 (BACKFLUSH) and
T3 (RESET) to actuate the valve. For the second analysis use
times T2 (BACKFLUSH) and T4 (RESET) to actuate the
valve.
NOTE 2—The first analysis is used to calibrate the gas chromatograph
for benzene and toluene. The second analysis is used to calibrate for FIG. 3 Typical Benzene Calibration Curve
ethylbenzene, the xylenes (o-xylene), and the C9 and heavier aromatics
(1,2,4-trimethylbenzene).
11.4.1 Linearity Test—Analyze the calibration standards x 5 X i 2 x̄ (5)
y 5 Yi 2 ȳ (6)
in accordance with the procedure in 11.4. Measure the peak
areas of benzene, toluene, and internal standard peaks from the and:
first analysis. From the second analysis measure the peak areas X i = amti ratio data point,
of internal standard, ethylbenzene, o-xylene, and 1,2,4- x̄ = average values for all amti data points,
trimethylbenzene. Determine the response ratio (rspi) and Yi = corresponding rspi ratio data point, and
amount ratio (amti) for each component in each standard using ȳ = average values for all rspi data points.
Eq 2 and Eq 3. 11.4.1.3 Table 3 gives an example on the calculation of r2
for an ideal data set.
rspi 5 ~Ai/As! (2)
11.4.2 Linear Least Square Fit—For each aromatic i cali-
where: bration data set, obtain the linear least square fit equation in the
Ai = area of aromatic component, and form:
As = area of internal standard. ~rspi! 5 ~mi!~amti! 1 b i (7)
amti 5 ~Wi/Ws! (3)

where: TABLE 3 Example of Data Set for r2 CalculationA

Wi = mass of aromatic component, and
Xi Yi x = Xi − x̄ y = Yi − ȳ xy x2 y2
Ws = mass of internal standard.
11.4.1.1 Prepare a calibration curve for each aromatic com- 1.0 0.5 −2.0 1.0 2.0 4.0 1.0
2.0 1.0 −1.0 −0.5 0.5 1.0 0.25
ponent by plotting the response ratios (rspi), as the y-axis, 3.0 1.5 0.0 0.0 0.0 0.0 0.0
versus the amount ratios (amti), as the x-axis. Fig. 3 is an 4.0 2.0 1.0 0.5 0.5 1.0 0.25
example of such a plot. 5.0 2.5 2.0 1.0 2.0 4.0 1.0

11.4.1.2 Calculate the correlation coefficient r2 value for A

x̄ = 3
ȳ = 1.5
each aromatic component in the calibration using Eq 4. The r2 (( xy)2= 25.0
value should be at least 0.990 or greater. If the above criteria ( x2= 10.0
for r2 is not met, rerun the calibration or check instrument ( y2= 2.5
~ ( x·y!2
parameters and hardware. r2=
~ ( x 2!·~ ( y2!
~ ( xy!2 25.0
r2 5 (4) r2= 5 1.0
~ ( x2!~ ( y2! ~10.0!~2.5!

where:

6
 D 5580

where: 12. Column Conditioning

rspi = response ratio for aromatic i ( y-axis), 12.1 Both the TCEP and WCOT columns are to be briefly
mi = slope of linear equation for aromatic i, conditioned before use. Connect the columns to the valve (see
amti = amount ratio for aromatic i (x-axis), and
Fig. 1 and 10.1) in the chromatographic oven. Adjust the
bi = y-axis intercept.
carrier gas flows in accordance with 10.3 and place the valve in
11.4.2.1 The values mi and bi are calculated as follows: the RESET position. After several minutes, increase the col-
mi 5 ( xy/( x 2 (8) umn oven temperature to 120°C and maintain these conditions
for 20 min. Cool the columns below 60°C before shutting off
and:
the carrier gas.
bi 5 ȳ 2 mi x̄ (9)
11.4.2.2 For the example in Table 3 13. Procedure
mi 5 5/10 5 0.5 (10) 13.1 Preparation of Sample—Transfer 1 mL of internal
and standard (Ws) by a volumetric pipette into a tared and capped
10-mL volumetric flask or capped vial. Record the net mass of
bi 5 1.5 2 ~0.5!~3! 5 0 (11) the internal standard added to the nearest 0.1 mg. Retare the
11.4.2.3 Therefore, the least square equation (Eq 7) for the capped flask or vial. Fill the volumetric flask or vial with 9 mL
example in Table 3 is: of chilled sample, cap, and record the net mass (Wg) of the
~rspi! 5 0.5~amti! 1 0 (12) sample added. Mix thoroughly. If using an automatic sampler
then transfer an aliquot of the solution into a glass GC vial.
NOTE 3—Normally the bi value is not zero and can be positive or Seal the GC vial with a TFE-fluorocarbon-lined cap. If the
negative. Fig. 3 gives an example of linear least square fit for benzene and sample is not immediately analyzed, store at 0 to 5°C (32 to
the resulting equation in the Eq 7.
40°F).
11.4.3 Y-Intercept Test—For an optimum calibration, the 13.2 Chromatographic Analysis—Introduce an aliquot of
absolute value of the y-intercept (bi) must be at a minimum. In the sample, containing internal standard, into the gas chromato-
this case, Ai approaches zero when wi is less than 0.1 mass %. graph using the same technique and sample size as used for the
In practice, this means the mass % (wi) calculated for an calibration analysis. An injection volume of 1 µL with a 11:1
aromatic with zero peak area must be close to zero. The split ratio has been used successfully. Chromatograph the
equation to determine the mass % aromatic i, or wi, reduces to sample twice using valve timing procedures in accordance with
Eq 13. The y-intercept can be tested using 13 below: 10.5. Use times T1 and T3 for the first analysis to BACK-
wi 5 ~b i / mi!~Ws/Wg!100 % (13) FLUSH and RESET the valve. Use times T2 and T4 for the
second analysis.
where: 13.3 Interpretation of Chromatogram— Compare the reten-
wi = mass % aromatic i, tion times of sample components to those of the calibration
Ws = mass of internal standard added, g, and
analysis to determine the identities of the aromatics. Identify
Wg = mass of gasoline samples, g.
benzene, toluene, and the internal standard from the first
NOTE 4—Since in practice Ws and Wg vary slightly from sample to analysis. Identify the internal standard, ethylbenzene, p/m-
sample, use an average value as indicated below. xylene, o-xylene, C9 and heavier aromatic composite from the
For benzene, wi must be less than 0.02 mass %. For the other second analysis. Refer to Fig. 4 and Fig. 5 for sample
aromatics, wi must be less than 0.2 mass %. If any of the wi chromatograms.
values exceed the mass % limit, rerun the calibration procedure NOTE 5—Gasolines containing styrene will have an additional peak in
for aromatic i, or check instrument parameters and hardware. the chromatogram. Styrene elutes just before o—xylene; the two peaks are
The following gives an example of the calculation for the partially, but not baseline, resolved. If quantitation of sytrene is desired,
y-intercept (bi) test using the data from Fig. 3 for aromatic i use the o-xylene calibration.
(benzene) for which bi = 0.0018 and mi = 1.41. From 13.1, a
14. Calculation and Report
typical sample preparation may contain approximately Ws
= 0.8 g (1.0 mL) of internal standard and Wg = 6.75 g (9.0 14.1 Mass Concentration of Aromatics— After identifying
mL) of a gasoline sample. Substituting these values into Eq 13 the peaks, measure the areas of benzene, toluene, and the
yields: internal standard from the first analysis and the internal
wi 5 ~0.0018/1.41!~0.8/6.75!100 % (14) standard, ethylbenzene, p/m-xylene, o-xylene, C9 and heavier
aromatics from the second analysis. Using the slope and
wi 5 0.01 mass %
y-intercept of the least square fit calibrations in 11.4.2, calcu-
Since wi is less than 0.02 mass% , the y-intercept (bi) has an late the mass of each aromatic component (Wi) in the gasoline
acceptable value for benzene. Similarly, determine wi for all samples using the response ratio (rspi) of the areas of the
other aromatics. aromatic component to the internal standard as follows:

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 D 5580

FIG. 4 Aromatics in Gasoline, Analysis No. 1

FIG. 5 Aromatics in Gasoline, Analysis No. 2

Wi 5 FS Ai
D G
As 2 bi /m i Ws (15) wi 5
Wi~100!
Wg (16)

where: where:
Wi = mass of aromatic component i, Wg = mass of gasoline sample.
Ai = area of aromatic component i, 14.1.2 Report the mass percent (wi) results of the following
As = area of internal standard, and
aromatics to the nearest 0.01 %; benzene, toluene, ethylben-
Ws = mass of internal standard added.
zene, p/m-xylene, o-xylene, C9 and heavier aromatics.
14.1.1 To obtain mass percent (w i) results for each compo-
nent:

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 D 5580
14.1.3 To obtain the total mass percent aromatics, sum the 15.1.1 Repeatability—The difference between successive
mass percent (wi) results of all the individual aromatic com- test results obtained by the same operator with the same
ponents i. apparatus under constant operating conditions on identical test
14.2 Volumetric Concentration of Aromatic materials would, in the long run, in the normal and correct
Components—If the volumetric concentration of each aromatic operation of the test method exceed the following values in
component i is desired, calculate the volumetric concentration only one case in twenty. See Table 4.
in accordance with Eq 15: 15.1.2 Reproducibility—The difference between two single
S D
Df
v i 5 wi D
i
(17) and independent results obtained by different operators work-
ing in different laboratories on identical material, would in the
where: long run, exceed the following values in one case in twenty.
vi = volume percent of each aromatic component to be See Table 5.
determined, 15.1.3 Bias—Since there is no accepted reference material
Df = relative density of the fuel under study as determined suitable for determining bias for the procedure in this test
in accordance with Test Method D 1298 or Test method, no statement of bias is being made.
Method D 4052, and
Di = relative density at 15.56°C (60°F) of the individual 16. Keywords
aromatics (Table 2).
14.2.1 Report the volume percent results ( vi) of the follow- 16.1 aromatics; benzene; ethylbenzene; gas chromatogra-
ing aromatic components to the nearest 0.01 %; benzene, phy; gasoline; toluene; xylenes
toluene, ethylbenzene, p/m-xylene, o-xylene, and C9 and
heavier aromatics.
14.2.2 To obtain total volume percent aromatics, sum the
volume percent (vi) results of all the individual aromatic
components i. TABLE 4 Repeatability Estimates for Aromatics in Gasoline
Range,
15. Precision and Bias 5 Component
(mass %)
Repeatability (X = mass % )

15.1 Precision—The precision of this test method as deter- Benzene 0.14–1.79 0.0265(X0.65)
mined by the statistical examination of the interlaboratory test Toluene 2.11–10.08 0.0301(X0.5)
reports is as follows:5 Ethylbenzene 0.57–2.65 0.029
P/M-xylene 2.06–9.59 0.071
O-xylene 0.77–3.92 0.0296(X0.5)
C9 plus aromatics 8.32–25.05 0.0145(X+5.157)
5
Supporting data are available from ASTM International Headquarters. Request Total aromatics 16.34–49.07 0.0899(X0.5)
RR: D02-1329.

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 D 5580
TABLE 5 Reproducibility Estimates for Aromatics in Gasoline TABLE 6 Volume % Precision for Benzene and Total AromaticsA
Range, Reproducibility Range,
Component Repeatability Reproducibility
(mass %) (X = mass % ) (Volume %)
0.65 0.64
Benzene 0.14–1.79 0.1229(X ) Benzene 0.11–1.5 0.0259(X ) 0.1087(X0.64)
Toluene 2.11–10.08 0.0926(X0.5) Total Aromatics 14–43 0.0825(X0.5) 0.2619(X0.5)
Ethylbenzene 0.57–2.65 0.163 A
The precision in Table 6 was obtained with a constant sample density for each
P/M-xylene 2.06–9.59 0.452
sample provided to the round robin participants to covert mass % to volume %.
O-xylene 0.77–3.92 0.1168(X0.5)
C9 plus aromatics 8.32–25.05 0.070(X+5.157)
Total aromatics 16.34–49.07 0.2851(X0.5)

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