Astm D6729 01

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An American National Standard

Designation: D 6729 – 01
Standard Test Method for

Determination of Individual Components in Spark Ignition
Engine Fuels by 100 Meter Capillary High Resolution Gas
Chromatography1
This standard is issued under the fixed designation D 6729; 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 boiling cuts such as those derived from fluid catalytic cracking
1.1 This test method covers the determination of individual (FCC) are analyzed, and the total olefin content may not be
hydrocarbon components of spark-ignition engine fuels and accurate.
their mixtures containing oxygenate blends (MTBE, ETBE, 1.4.1 Total olefins in the samples may be obtained or
ethanol, and so forth) with boiling ranges up to 225°C. Other confirmed, or both, if necessary, by Test Method D 1319
light liquid hydrocarbon mixtures typically encountered in (volume %) or other test methods, such as those based on
petroleum refining operations, such as blending stocks (naph- multidimensional PONA type of instruments.
thas, reformates, alkylates, and so forth) may also be analyzed; 1.5 If water is or is suspected of being present, its concen-
however, statistical data was obtained only with blended tration may be determined, if desired, by the use of Test
spark-ignition engine fuels. Method D 1744, or equivalent. Other compounds containing
1.2 Based on the cooperative study results, individual com- oxygen, sulfur, nitrogen, and so forth, may also be present, and
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ponent concentrations and precision are determined in the
range of 0.01 to approximately 30 mass %. The procedure may
may co-elute with the hydrocarbons. If determination of these
specific compounds is required, it is recommended that test
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be applicable to higher and lower concentrations for the methods for these specific materials be used, such as Test
individual components; however, the user must verify the Methods D 4815 and D 5599 for oxygenates, and D 5623 for
accuracy if the procedure is used for components with concen- sulfur compounds, or equivalent.
trations outside the specified ranges. Document Preview
1.3 The test method also determines methanol, ethanol,
1.6 Annex A1 of this test method compares results of the
test procedure with other test methods for selected compo-
t-butanol, methyl t-butyl ether (MTBE), ethyl t-butyl ether nents, including olefins, and several group types for several
(ETBE), t-amyl methyl ether (TAME) in spark ignitionASTM interlaboratory cooperative study samples. Although benzene,
engine D6729-01
fuels in the concentration range of 1 to 30 mass %. However, toluene, and several oxygenates are determined, when doubtful
https://standards.iteh.ai/catalog/standards/sist/23b95bb7-47b6-4e38-bcf4-e3f0eccdfbcc/astm-d6729-01
the cooperative study data provided sufficient statistical data as to the analytical results of these components, confirmatory
for MTBE only. analyses can be obtained by using specific test methods.
1.4 Although a majority of the individual hydrocarbons 1.7 The values stated in SI units are to be regarded as the
present are determined, some co-elution of compounds is standard. The values given in parentheses are provided for
encountered. If this test method is utilized to estimate bulk information purposes only.
hydrocarbon group-type composition (PONA) the user of such 1.8 This standard does not purport to address all of the
data should be cautioned that some error will be encountered safety concerns, if any, associated with its use. It is the
due to co-elution and a lack of identification of all components responsibility of the user of this standard to establish appro-
present. Samples containing significant amounts of olefinic or priate safety and health practices and determine the applica-
naphthenic (for example, virgin naphthas), or both, constitu- bility of regulatory limitations prior to use.
ents above n-octane may reflect significant errors in PONA 2. Referenced Documents
type groupings. Based on the gasoline samples in the inter-
laboratory cooperative study, this procedure is applicable to 2.1 ASTM Standards:
samples containing less than 25 mass % of olefins. However, D 1319 Test Method for Hydrocarbon Types in Liquid
some interfering coelution with the olefins above C7 is pos- Petroleum Products by Fluorescent Indicator Adsorption2
sible, particularly if blending components or their higher D 1744 Test Method for Determination of Water in Liquid
Petroleum Products by Karl Fisher Reagent3
1
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products and Lubricantsand is the direct responsibility of Subcommittee
2
D02.04 on Hydrocarbon Analysis. Annual Book of ASTM Standards, Vol 05.01.
3
Current edition approved Nov. 10, 2001. Published January 2002. Discontinued; see 1999 Annual Book of ASTM Standards, Vol 05.01.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
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D 6729
D 4815 Test Method for Determination of MTBE, ETBE, 6.2 Inlet—a capillary split/splitless inlet system operated in
TAME, DIPE, t-Amyl Alcohol and C1 to C4 Alcohols in the split mode is recommended. It must be operated in its linear
Gasoline by Gas Chromatography4 range. Refer to 8.4 to determine the proper split ratio.
D 5599 Test Method for Determination of Oxygenates in 6.2.1 Carrier Gas Pneumatic Control—Constant carrier gas
Gasoline by Gas Chromatography and Oxygen Selective pressure control was used by all cooperative study participants.
Flame Ionization Detection4 This may be either direct pressure to the inlet (injector) or by
D 5623 Test Method for Sulfur Compounds in Light Petro- using a total flow/back pressure system.
leum Liquids by Gas Chromatography and Sulfur Selec- 6.2.2 Pneumatic Operation of the Chromatograph—The
tive Detection4 use of constant pressure was the mode of operating the gas
E 355 Practice for Gas Chromatography Terms and Rela- chromatography used by the participants in the interlaboratory
tionships5 cooperative study. Other carrier gas control methods such as
constant flow (pressure programming) may be used, but this
3. Terminology may change the chromatography elution pattern unless the
3.1 Definitions—This test method makes reference to many temperature programming profile is also adjusted to compen-
common gas chromatographic procedures, terms, and relation- sate for the flow differences.
ships. Detailed definitions can be found in Practice E 355. 6.2.3 Temperature Control—The injector operated in the
split mode shall be heated by a separate heating zone and
4. Summary of Test Method heated to temperatures of 200 to 275°C.
4.1 Representative samples of the petroleum liquid are 6.3 Column, a fused silica capillary column, 100 m in length
introduced into a gas chromatograph equipped with an open by 0.25 mm inside diameter, coated with a 0.5 mm film of
tubular (capillary) column coated with the specified stationary bonded dimethylpolysiloxane. The column must meet the
phase. Helium carrier gas transports the vaporized sample resolution requirements expressed in 8.3. Columns from two
through the column, in which it is partitioned into individual different commercial sources were used in the interlaboratory
components which are sensed with a flame ionization detector cooperative study.
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as they elute from the end of the column. The detector signal 6.4 Data System, a computer based chromatography data
is recorded digitally by way of an integrator or integrating system capable of accurately and repeatedly measuring the
retention time and areas of eluting peaks. The system shall be
computer. Each eluting component is identified by comparing
its retention time to that established by analyzing reference able to acquire data at a rate of at least 10 Hz. Although it is not
standards or samples under identical conditions. The concen- mandatory, a data system which calculates column resolution
Document Preview
tration of each component in mass % is determined by
normalization of the peak areas after correction of selected
(R) is extremely useful as it will replace the need to carry out
the manual calculations which must be performed as listed in
8.3.
components with detector response factors. The unknown
components are reported individually and as a summary total. 6.4.1 Electronic Integrators, shall be capable of storing up
ASTM D6729-01
to 400 components in the peak table and shall be able to
5. Significance and Use acquire the data at 10 Hz or faster speeds. They shall be
capable of integrating peaks having peak widths at half height
5.1 Knowledge of the specified individual component com-
which are 1.0s wide. The integrator must be capable of
position (speciation) of gasoline fuels and blending stocks is
displaying the integration mode of partially resolved peaks. In
useful for refinery quality control and product specification.
addition, these integrators should be able to download a
Process control and product specification compliance for many
commonly readable format of data (that is, ASCII) to a
individual hydrocarbons may be determined through the use of
computer in order to facilitate data processing.
this test method.
6.5 Sample Introduction—Sample introduction by way of a
6. Apparatus valve, automatic injection device, robotic arm or other auto-
matic means is highly recommended. An automatic sample
6.1 Gas Chromatograph, a gas chromatograph equipped introduction device is essential to the reproducibility of the
with cryogenic column oven cooling and capable of producing analysis. Manual injections are not recommended. All of the
repeatable oven ramps from 0° to at least 300°C is required. reproducibility data reported by this test method for the
The following features are useful during the sample analysis samples analyzed were gathered using automatic injection
phase: electronic flow readout, electronic sample split-ratio devices.
readout, and electronic pneumatic control of flow. Though their 6.6 Flame Ionization Detector (FID)—The gas chromato-
use is not required, careful review of this test method will graph should possess a FID having a sensitivity of 0.005
demonstrate the usefulness of a gas chromatograph equipped coulombs/g for n-butane. The linear dynamic range of the
with these features. These features will replace the need to detector should be 106 or better. The detector is heated to
carry out the manual calculations that must be performed as 300°C.
listed in 8.1 and 8.2.
7. Reagents and Materials
7.1 Calibrating Standard Mixture—A spark ignition engine
4
Annual Book of ASTM Standards, Vol 05.03. fuel standard of known composition and concentration by mass
5
Annual Book of ASTM Standards, Vol 14.02. can be used. In order to corroborate the identification of the
2
D 6729
sample, a typical chromatogram (Fig. 1) was obtained from 7.2 Gas Chromatograph Gases—All of the following gases
reference sample ARC96OX.6 shall have a purity of 99.999 % (V/V) or greater.
NOTE 1—Warning: Gases are compressed. Some are flammable and all
gases are under high pressure.
6
Reference spark ignition sample No. ARC 960X obtained from the Alberta
Research Council, Edmonton, Alberta, Canada. Other samples are available from
7.2.1 Helium—The test data was developed with helium as
suppliers. the carrier gas. It is possible that other carrier gases may be
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ASTM D6729-01
FIG. 1 Chromatogram for Reference Spiked Gasoline
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D 6729
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ASTM D6729-01
FIG. 1 Chromatogram for Reference Spiked Gasoline (continued)
used for this test method. At this time, no data is available from 8. Instrument Check Out Prior to Analysis
this test method with other carrier gases.
8.1 Setting:
7.2.2 Air, Hydrogen and Make-up Gas (Helium or Nitro-
gen), shall have a purity of 99.999 % (V/V) or greater.
4
D 6729
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ASTM D6729-01
8.1.1 Linear Gas Velocity—If the gas chromatograph is linear velocity of 25 to 26 cm/s. This is equivalent to retention
equipped with an electronic flow readout device, set the flow to times of methane at 0°C ranging from 6.5 to 6.8 min.
1.8 mL/min. This is achieved by setting the carrier gas flow 8.1.2 If the gas chromatograph is not equipped with an
rate by injection of methane or natural gas at 35°C. Ensure that electronic flow readout device, calculate the linear gas velocity
the retention time is 7.00 6 0.05 min. This corresponds to a in cm/s using Eq 1.
5
D 6729
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ASTM D6729-01
column length ~cm! split ratio to a sample split of 200:1. If the gas chromatograph
linear gas velocity 5 V 5 retention time of methane~s! (1)
is not equipped with an electronic split-ratio readout device,
8.1.3 The typical retention times for methane and linear gas one must first calculate column flow rate and then proceed to
velocity for helium are 6.5 to 6.8 and 24 to 26 cm/s, calculating split ratio using Eq 2 and 3.
respectively.
~60 p r2! L~Tref! 2~Pi – Po!
8.2 Setting the Split Ratio—If the gas chromatograph is column flow rate 5 F 5 (2)
~T!3~Pref!~Pi2 – Po2!µ
equipped with an electronic split-ratio readout device, set the
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D 6729
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ASTM D6729-01
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ASTM D6729-01
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ASTM D6729-01
where: Po = outlet pressure,

F = flow rate as calculated by using the equation, Pref = reference pressure, 1 atm,
r = column radius, cm, T = temperature of the column oven,
L = column length, cm, Tref = temperature at the column outlet, and
Pi = inlet pressure, µ = linear velocity, cm/s.
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D 6729
split vent flow 1 F TABLE 2 Resolution Performance Requirements
split ratio 5 S 5 F (3)
Component Minimum Concentration of Each
Pair Resolution Component, W/W
8.2.1 The column flow rate is calculated by the use of Eq 2.
Benzene 1.0 0.5 %–0.5 %
Use the results obtained from Eq 3 to adjust the split flow until
1-Methyl-cyclopentene
a split flow of approximately 200:1 is achieved. m-Xylene 0.4 2.0 %–2.0 %
8.3 Evaluation of Column Performance: p-Xylene
n-Tridecane 1.0 0.5 %–0.5 %
8.3.1 Prior to using the column described in Table 1, 1-Methylnaphthalene
measure the resolution of the column under the conditions of
Table 2. Check that the resolution for the following pairs of
components is obtained using Eq 4 to calculate the resolution
of a pair of components: 8.3.3 Subtract the baseline from a sample chromatogram
and verify that the residual signal at the beginning of the
~tR2 – tR1!2 chromatogram does not differ from the end of the chromato-
R5 (4)
1.699 ~Wh1 1 Wh2! gram by more than 2 %.
where: 8.4 Evaluation of Splitter Linearity—Using the reference
R = resolution, gasoline sample, inject this sample according to the schedule
tR2 = retention time of the first member of the pair, listed in Table 3.
tR1 = retention time of the second member of the pair, 8.4.1 Select from the chromatogram about 10 to 15 compo-
Wh1 = peak width at half height of the first member of the nents, which have concentrations in the range of .01 to 30
pair, and weight %. Tabulate for each split ratio the concentrations of the
Wh2 = peak width at half height of the second member of 10 to 15 components. Verify that for each component selected,
the pair. its concentration does not vary by more than 3 %.
8.3.1.1 Column resolution should be checked frequently by
examining the resolution of these compounds. 9. Procedure
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8.3.2 Evaluation of the Baseline—Carry out a blank base- 9.1 Set the operating conditions of the gas chromatograph as
line run utilizing no solvent injection, by setting the GC in shown in Table 1. These conditions will elute all components
accordance with the conditions of Table 1. up to and including pentadecane (nC15).
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TABLE 1 Chromatographic Operating Conditions, Column Requirements and Data Acquisition Requirements
Chromatographic Conditions Requirements
Injector settings
Injector temperature, °C 250
Split ratio ASTM D6729-01 175:1 - 275:1
Liner deactivated glass
Injection volume, µL 0.2–0.5
Detector settings
FID detector temperature, °CA 300–350
Gas flows
Hydrogen, mL/minB 30–40
Air, mL/min 300–450
Nitrogen make up, mL/min 30
Column oven settings
Initial temperature, °C 0
Initial time, min 15
1st ramp rate, °C/min 1
Final temperature, °C 50
Final time, min 0
2nd ramp rate, °C/min 2
Final time, min 0
3rd ramp rate, °C/min 4
Final time, minC 0
Column Requirements
Length, m 100
Inside diameter, mm 0.25
Liquid phase 100 % dimethylpolysiloxane
Film thickness, µ 0.5
Pressure, psig 40–50
Flow, mL/min 1.7–2.0
Linear gas velocity, cm/s 24.5
Data acquisition, Hz 10–20
Total analysis time, min 140–150
A
Set to 25–50°C above the highest column temperature.
B
Values to be set as recommended by instrument manufacturer.
C
Final temperature or time may be adjusted to ensure complete elution of the sample components.
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D 6729
TABLE 3 Injection Schedule 10. Data Analysis
Injection Volume, Injection Temperature,
Split Ratio
µL °C 10.1 Compound Identification—Prepare a table listing all of
100:1 0.1 250
the retention times of the components in the sample. Compare
200:1 0.5 250 the retention time of each peak with that of the reference
300:1 1.0 250 gasoline. Pay particular attention to the fact that columns can
be overloaded, and peaks can shift in retention time. Observe
the peak pattern so that proper identification is made by
comparison with the reference material.
9.2 All of the parameters in Table 1 can be marginally 10.2 Consistency in peak identification can be achieved by
changed to optimize for sample types and optimize for char- using software (data handling software, spreadsheet software,
acteristics of each gas chromatographic system. The final and so forth). Alternatively, a retention index system can be
boiling point of samples should not exceed nC15 and the used.
column resolution (R) performance requirements listed in
Table 2 should not be compromised.
9.3 Obtain a representative sample following the guidelines
~R1!i 5 100n 1 100
log ~Ti! – log ~Tn!
log ~TN! – log ~Tn! F (5) G
of Practice D 4057 and any other applicable guidelines. Take where:
precautions to minimize the loss of light ends from volatile (R1)i = retention index of component I bracketed by the
samples. The sample container may be cooled prior to transfer N-paraffin, n in its lower boundary and N-paraffin N
of sample into it. Cool the sample to less than 4°C, maintain at in its upper boundary,
that approximate temperature until the autosampler is loaded Ti = adjusted retention time of component i (retention
and analysis begins. time of component i minus the retention time of
9.4 Preparation/Storage: methane),
9.4.1 Samples Stored in Vials—Cool the original sample to Tn = adjusted retention time of N-paraffin n, and
less than 4°C prior to taking a sample aliquot or prior to filling TN = retention time of N-paraffin N.
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the sample vials. The sample aliquot container, or the vial, or
both, can also be cooled prior to the transfer of the original
10.3 Determine the hydrocarbon response factors by using
the following equation.7
sample. Syringes may also be cooled along with the sample for MWi 1
manual injections. RRFCH4 5 N 3 MW (6)
c CH4
9.4.2 Samples Stored in Pressurized Containers—It is rec-
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ommended that they be kept away from direct heat or light. No
other sample preparations are necessary for samples stored in
where:
RRFCH4 = relative response factor of each component
pressurized containers. Avoid storage at temperatures greater with respect to methane (RRFCH4=1.000),
than 25°C. Store pressure containers in accordance with the MWi = molecular weight of the component, i,
ASTM D6729-01
Nc = number of carbon atoms in the molecule, and
manufacturer’s instructions.
9.5 It is recommended that a quality assurance (QA) sample MW CH4 = molecular weight of methane (16.04276).
similar to the reference material gasoline sample be run at 10.4 Convert the acquired areas to corrected areas by
regular intervals (see Fig. 1). An interval of once per week or multiplying each area by its corresponding relative response
after every 15 samples is recommended. The quantitation factor as indicated in the following equation.
results use statistical quality control charts can track benzene. Ac 5 ~A!I ~RRF!I i
(7)
Other components of interest in the reference sample can be
tracked in a similar manner. By monitoring these components
over an extended period of time, the performance of the
column and the chromatographic system can be determined. 7
Sevcik, J., Detectors in Gas Chromatography, Elsevier, NY, 1976, p 94.
TABLE 4 Predominant Compounds and Identified Coeluting CompoundsA
NOTE—The response factor of the predominant compound will be used for the analyte and this analyte will be used for the calculations.
Peak Number Predominant Coeluting
(from Annex A1) Compound Compound(s)
164 3,3-dimethylpentane 5-methyl-1-hexene
186 2-methylhexane C7-olefin
278 2,5-dimethylhexane C8-olefin
286 3,3-dimethylhexane C8-olefin
304 toluene 2,3,3-trimethylpentaneB
324 1,1,2-trimethylcyclopentane C7-triolefin
326 C8-diolefin C8-paraffin
492 4-methyloctane C9-olefin
796 1,2,3,4-tetramethylbenzene C11-aromatic
A
This is not an exhaustive list. Due to the possibility of coeluting peaks in other areas, the user is cautioned in the interpretation of the data.
B
In most alkylated gasolines, a split may occur between toluene and 233 TMC5.
11

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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.

Contact ASTM International (www.astm.org) for the latest information

An American National Standard

Standard Test Method for

FIG. 1 Chromatogram for Reference Spiked Gasoline

FIG. 1 Chromatogram for Reference Spiked Gasoline (continued)

FIG. 1 Chromatogram for Reference Spiked Gasoline (continued)

FIG. 1 Chromatogram for Reference Spiked Gasoline (continued)

FIG. 1 Chromatogram for Reference Spiked Gasoline (continued)

FIG. 1 Chromatogram for Reference Spiked Gasoline (continued)

FIG. 1 Chromatogram for Reference Spiked Gasoline (continued)

where: Po = outlet pressure,

TABLE 4 Predominant Compounds and Identified Coeluting CompoundsA

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