Designation: D6296 − 98 (Reapproved 2008)

Standard Test Method for

Total Olefins in Spark-ignition Engine Fuels by
Multidimensional Gas Chromatography1
This standard is issued under the fixed designation D6296; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope 2. Referenced Documents

1.1 This test method provides for the quantitative determi- 2.1 ASTM Standards:2
nation of total olefins in the C4 to C10 range in spark-ignition D1319 Test Method for Hydrocarbon Types in Liquid Petro-
engine fuels or related hydrocarbon streams, such as naphthas leum Products by Fluorescent Indicator Adsorption
and cracked naphthas. Olefin concentrations in the range from D4052 Test Method for Density, Relative Density, and API
0.2 to 5.0 liquid-volume % or mass %, or both, can be Gravity of Liquids by Digital Density Meter
determined directly on the as-received sample whereas olefins D4307 Practice for Preparation of Liquid Blends for Use as
in samples containing higher concentrations are determined Analytical Standards
after appropriate sample dilution prior to analysis. D4815 Test Method for Determination of MTBE, ETBE,
1.2 This test method is applicable to samples containing TAME, DIPE, tertiary-Amyl Alcohol and C1 to C4 Alco-
alcohols and ethers; however, samples containing greater than hols in Gasoline by Gas Chromatography
15 % alcohol must be diluted. Samples containing greater than D5599 Test Method for Determination of Oxygenates in
5.0 % ether must also be diluted to the 5.0 % or less level, prior Gasoline by Gas Chromatography and Oxygen Selective
to analysis. When ethyl-tert-butylether is present, only olefins Flame Ionization Detection
in the C4 to C9 range can be determined. 3. Terminology
1.3 This test method can not be used to determine individual 3.1 Definitions of Terms Specific to This Standard:
olefin components. 3.1.1 trap, n—a device utilized to selectively retain specific
1.4 This test method can not be used to determine olefins portions (individual or groups of hydrocarbons or oxygenates)
having higher carbon numbers than C10. of the test sample and to release the retained components by
increasing the trap temperature.
NOTE 1—Precision was determined only on samples containing MTBE
and ethanol. 3.2 Acronyms:
1.5 The values stated in SI units are to be regarded as 3.2.1 ETBE—ethyl-tert-butylether.
standard. No other units of measurement are included in this 3.2.2 MTBE—methyl-tert–butylether.
standard.
4. Summary of Test Method
1.6 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the 4.1 A reproducible 0.2-µL volume of a representative
responsibility of the user of this standard to establish appro- sample, or a dilution thereof, is introduced into a computer
priate safety and health practices and determine the applica- controlled gas chromatographic system3 consisting of a series
bility of regulatory limitations prior to use.
2
For referenced ASTM standards, visit the ASTM website, [Link], or
contact ASTM Customer Service at service@[Link]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
1
This test method is under the jurisdiction of ASTM Committee D02 on the ASTM website.
3
Petroleum Products and Lubricantsand is the direct responsibility of Subcommittee The sole source of supply of apparatus known to the committee at this time, the
D02.04.0L on Gas Chromatography Methods. AC FTO Analyzer, is AC Analytical Controls, Inc., 3494 Progress Dr., Bensalem,
Current edition approved May 1, 2008. Published September 2008. Originally PA 19020. If you are aware of alternative suppliers, please provide this information
approved in 1998. Last previous edition approved in 2003 as D6296–98(2003)´1. to ASTM Headquarters. Your comments will receive careful consideration at a
DOI: 10.1520/D6296-98R08. meeting of the responsible technical committee,1 which you may attend.

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

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 D6296 − 98 (2008)

FIG. 1 Typical Flow Diagram and Component Configuration

of columns, traps, and switching valves operating at various 5.2 Knowledge of the total olefin content provides a means
temperatures. The valves are actuated at predetermined times to monitor the efficiency of catalytic cracking processes.
to direct portions of the sample to appropriate columns and 5.3 This test method provides better precision for olefin
traps. The sample first passes through a polar column that content than Test Method D1319. It also provides data in a
retains C12+ hydrocarbons, all aromatics, C11+ olefins, and much shorter time, approximately 20 min following calibra-
some alcohols, all of which are subsequently backflushed to tion, and maximizes automation to reduce operator labor.
vent. The fraction eluting from the polar column, which
contains C11 and lower boiling saturated hydrocarbons as well 5.4 This test method is not applicable to M85 or E85 fuels,
as decene and lower boiling olefins, enters an ether/alcohol trap which contain 85 % methanol and ethanol, respectively.
where the ethers and alcohols are selectively retained and also
subsequently backflushed. The fraction eluting from the ether/ 6. Interferences
alcohol trap, which consists of C11 and lower boiling saturated 6.1 Some types of sulfur-containing compounds are irre-
hydrocarbons and the olefins, enters an olefin trap. The olefins versibly absorbed in the olefin and oxygenate traps ultimately
are selectively retained while the saturated hydrocarbons elute, reducing the trap capacity. However, a variety of spark-ignition
pass through a nonpolar column, and are detected by a flame engine fuels have been analyzed without significant perfor-
ionization detector (FID). When the saturated hydrocarbons mance deterioration of these traps.
have completely eluted to the FID, the nonpolar column oven 6.2 Commercial dyes used to distinguish between grades
is cooled and the olefins, which have been retained on the and types of spark-ignition engine fuels have not been found to
olefin trap, are desorbed by heating. The desorbed olefins enter interfere with this test method.
and elute from the nonpolar column, which is temperature
programmed to separate the olefins by boiling point, and are 6.3 Commercial detergent additives utilized in spark-
detected by the FID. ignition engine fuels have not been found to interfere with this
test method.
NOTE 2—Separation of olefins by boiling point is necessary for the
calculation of the volume % of the olefins because the density of low 6.4 Dissolved water in spark-ignition engine fuels has not
boiling olefins differs from that of high boiling olefins and, therefore, a been found to interfere with this test method. Free water must
density correction must be applied. be removed using anhydrous sodium sulfate or other drying
4.2 Quantitation of the detected olefin peak areas to provide agent to permit injection of accurate sample volumes.
volume % or mass %, or both, is accomplished through the use
of an external standard followed by the application of flame 7. Apparatus
ionization detector response factors. The quantitation also 7.1 The complete system used to obtain the precision data is
takes into consideration the baseline compensation, sample comprised of a computer controlled gas chromatograph, auto-
dilution, and density corrections. mated sample injector, computer software, and specific hard-
ware modifications. These modifications include columns,
5. Significance and Use traps, and valves which are described as follows and in Section
5.1 The quantitative determination of olefins in spark- 8. Fig. 1 illustrates a typical flow diagram and component
ignition engine fuels is required to comply with government configuration. Other configurations, components, or conditions
regulations. may be utilized provided they are capable of separating the

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 D6296 − 98 (2008)
olefins and producing a precision that is equivalent, or better, TABLE 1 Temperature Control Ranges of System Components
than that shown in the table of precision data. Typical Operating
Temperature Heating Time, min, Cooling Time, min,
7.2 Gas Chromatograph, dual column, temperature pro- Component Range, °C max max
grammable over a range from 60 to 160°C at approximately Polar column 60 to 160 temperature
Nonpolar column 60 to 160 programmed, ; 20°C/min
20°C/min, equipped with heated flash vaporization sample Ether/alcohol trap 120 to 280 1 5
inlets, a single flame ionization detector, necessary flow Olefin trap 155 to 280 1 5
controllers, and computer control. Column switching 100 isothermal
Valves
7.3 Sample Introduction System , manual or automatic, Sample lines 100 isothermal
capable of injecting a reproducible 0.2-µL injection volume of
liquid. The total injected sample must be introduced to the
chromatographic system, thus excluding the use of split injec-
systems utilized must have the capability of operating at
tions or carrier gas purging of the inlet septum. An auto injector
temperatures 620° of those indicated to accommodate specific
is recommended but optional. The precision data was obtained
systems. Temperature control may be by any means that will
using an automated sample injector.
meet the requirements of Table 1.
7.4 Gas Flow and Pressure Controllers , with adequate
NOTE 4—The system components and temperatures listed in Table 1
precision to provide reproducible flow and pressure of helium and Section 8 are specific to the analyzer used to obtain the precision data.
to the chromatographic system, and hydrogen and air for the Other columns and traps that can adequately perform the required
flame ionization detector. Control of air flow for rapid cooling separations are also satisfactory but may require different temperatures.
of specific system components and for automated valve opera- 7.11 Valves, Column, and Trap Switching —automated
tion is also required. 6-port rotary valves are recommended. The valves must be
7.5 Electronic Data Acquisition System, must meet or ex- intended for gas chromatographic usage and meet the follow-
ceed the following specifications (see Note 3): ing requirements:
7.5.1 Capacity for 150 peaks for each analysis, 7.11.1 The valves must be capable of continuous operation
7.5.2 External standard calculation of selected peaks with at operating temperatures that will prevent sample condensa-
response factors and background correction, tion.
7.5.3 Noise and spike rejection capability, 7.11.2 The valves must be constructed of materials that are
7.5.4 Sampling rate for fast (<4.0 s.) peaks (>5 Hz to give nonreactive with the sample under analysis conditions. Stain-
20 points across peak), less steel, PFA, and Vespel4 are satisfactory.
7.5.5 Peak width detection for narrow and broad peaks, and 7.11.3 The valves must have a small internal volume but
7.5.6 Perpendicular drop. offer little restriction to carrier gas flow under analysis condi-
tions.
NOTE 3—Standard supplied software is typically satisfactory.
7.12 Valves, Air, to control pressurized air for ether/alcohol
7.6 Gas Purifiers, to remove moisture and oxygen from and olefin trap cooling; 3-port automated valves are recom-
helium, moisture and hydrocarbons from hydrogen, and mois- mended.
ture and hydrocarbons from air.
NOTE 5—New valves, tubing, columns, traps, and other materials that
7.7 Balance, analytical, capable of weighing 0.0001 g. contact the sample or gasses may require conditioning prior to operation
7.8 Glassware: in accordance with the manufacturer’s instructions.
7.8.1 Vial, autosampler, with caps and including a cap
8. Reagents and Materials
crimper (required when the recommended optional autosam-
pler is used). 8.1 Air, compressed, <10 mg/kg each of total hydrocarbons
7.8.2 Pipette, Pasteur, disposable, with bulb. and H2O. (Warning—Compressed gas under high pressure
7.8.3 Pipette, volumetric, graduated in 0.01 mL increments, that supports combustion.)
1- and 2-mL capacity. 8.2 Helium, 99.999 % pure, <0.1 mg/kg H2O (Warning—
7.8.4 Pipette, total volume, 1, 3, 5, 10, 20 and 25-mL Compressed gas under high pressure.)
capacity. 8.3 Hydrogen, 99.999 % pure, <0.1 mg/kg H2O
7.9 Septa, polytetrafluoroethylene (PTFE) lined for injector. (Warning—Extremely flammable gas under high pressure.)
7.10 Temperature Controllers of System Components—The 8.4 2,2,4-trimethylpenane (isooctane) , 99.99 % pure
independent temperature control of two columns and two traps, (Warning—Flammable. Harmful if inhaled.)
column switching valves, and sample lines is required. All 8.5 Columns and Traps (System Components) —This test
system components that contact the sample must be heated to method requires the use of two chromatographic columns and
a temperature that will prevent condensation of any sample two traps (see Note 4). Each system component is indepen-
component. Table 1 lists the system components and operating dently temperature controlled as described in 7.10 and Table 1.
temperature (see Note 4). Some of the components require Refer to Fig. 1 for the location of the components in the
isothermal operation, some require rapid heating and cooling,
while one requires reproducible temperature programming.
The indicated temperatures are typical; however, the control 4
PFA and Vespel are trademarks of E.I. DuPont de Nemours and Co.

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 D6296 − 98 (2008)
TABLE 2 Set Up Mixtures TABLE 3 Calibration Standard 1 Containing MTBE
Mixture Approximate Component Density, kg/L Mass % Volume %
No. Component Concentrations, mass % Pentene 0.6452 1.00 1.09
1 methyl-tert-butylether (MTBE) 5 Hexene 0.6763 1.00 1.04
isooctane 95 Heptene 0.7009 1.00 1.00
Octene 0.7186 1.00 0.98
2 ethyl-tert-butylether (ETBE) 5 Nonene 0.7329 1.00 0.96
isooctane 95 Decene 0.7440 1.00 0.94
Undecane 0.7438 1.00 0.94
Dodecane 0.7521 1.00 0.93
Isooctane 0.6985 87.00 87.41
MTBE 0.7451 5.00 4.71
system. The following list of columns and traps contains Total 100.00 100.00
guidelines that are to be used to judge suitability.
8.5.1 Polar Column—At a temperature of 160°C, this col-
umn must retain all aromatic components in the sample and TABLE 4 Calibration Standard 2 Containing ETBE
elute all nonaromatic components boiling below 200°C, which Component Density, kg/L Mass % Volume %
includes decene and lower boiling olefins, within 2 min after Pentene 0.6452 1.00 1.09
Hexene 0.6763 1.00 1.04
sample injection. Heptene 0.7009 1.00 1.00
[Link] This column must elute all aromatics and other Octene 0.7186 1.00 0.98
components retained from 8.5.1 within 8 min of when it is Nonene 0.7329 1.00 0.96
Decene 0.7440 1.00 0.94
backflushed. Decane 0.7335 1.00 0.95
8.5.2 Ether/Alcohol Trap—At a temperature of 140°C, this Undecane 0.7438 1.00 0.94
trap must retain alcohols and ethers and elute all non- Dodecane 0.7521 1.00 0.93
Isooctane 0.6985 86.00 86.45
oxygenates boiling below 200°C within 4.5 to 5.0 min after ETBE 0.7431 5.00 4.72
sample injection. Total 100.00 100.00
[Link] At a temperature of 280°C, this trap must elute all
retained components.
8.5.3 Olefin Trap—Within a temperature range from 140 to Standard 1 is used for all samples except those that contain
165°C, this trap must quantitatively retain (trap) all olefins in ETBE and Calibration Standard 2 is used for samples contain-
the C4 to C10 range for at least 10 min after sample injection ing ETBE. When the oxygenate composition of samples is
while eluting all non-olefin components boiling below 200°C. unknown, it can be determined using Test Method D4815,
[Link] At a temperature of 280°C, this trap must quantita- D5599, or other test methods. Mixtures may be purchased or
tively elute all trapped olefins. prepared according to Practice D4307. The actual concentra-
8.5.4 Nonpolar Column—At a temperature of 160°C, this tion levels are not critical but must be accurately known.
column must elute paraffins and naphthenes through C11 within Determine the density of the calibration standard by Test
2 min. Method D4052 or other test method.
[Link] This column must distribute the C4 through C10
olefins by carbon number when temperature programmed from 8.8 Quality Control Sample, used to routinely monitor the
60 to 160°C at approximately 20°C/min. operation of the chromatographic system and to verify that
reported concentrations are within the precision of the test
8.6 Set Up Mixtures—Two qualitative synthetic mixtures method. A sample or samples that are similar in composition to
containing isooctane and ethers are required to verify that all samples typically analyzed may be designated as the quality
instrument components, temperatures, and cut times are satis- control (QC) samples. When samples to be analyzed contain C4
factory to produce accurate analyses and to aid in making and C5 olefins, the QC samples must contain these to monitor
operating adjustments as columns and traps age. The compo- olefin trap capacity. Each QC sample must be of sufficient
sition of these mixtures and approximate component concen- volume to provide an ample supply for the intended period of
trations are shown in Table 2. The mixtures may be purchased use, and it must be homogeneous and stable under the
or prepared according to Practice D4307. (Warning— anticipated storage conditions.
Flammable. Harmful if inhaled.)
8.7 Calibration Standards—Quantitative synthetic mixtures 9. Preparation and Setup of Apparatus
of pure hydrocarbons and ethers (Warning—Flammable. 9.1 Assemble the analyzer system (gas chromatograph with
Harmful if inhaled) are required to verify that the required independent temperature controlled components) as shown in
component separation is being achieved, to determine the Fig. 1 or with an equivalent flow system. If using a commercial
retention time of the olefins by carbon number, and to system, install, place the system in service, and optimize the
determine the response factor on the FID for the olefins. system in accordance with the manufacturer’s instructions.
Examples of two mixtures, including densities of individual
NOTE 6—Commercial systems will have all parameters predetermined
components, are shown in Table 3 and Table 4.5 Calibration and accessible through the software. Other constructed systems will
require experimentation and optimization of parameters to achieve the
required separation and precision.
5
ASTM publication DS 4A, Physical Constants of Hydrocarbons , and ASTM
publication DS 4B, Physical Constants of Hydrocarbons for Oxygenates, ASTM 9.2 Impurities in the helium carrier gas, hydrogen, or air
International, W. Conshohocken, PA. will have a detrimental effect on the performance of the

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 D6296 − 98 (2008)

FIG. 2 Typical Chromatogram, Calibration Standard

columns and traps. Therefore, install efficient purifiers in the TABLE 5 Calculated Repeatability and Reproducibility for Total
Olefins
gas lines as close to the system as possible and use good quality
gases. The helium and hydrogen gas connection lines shall be Olefin Concentrations, Volume % Repeatability Reproducibility
1 0.1 0.3
made of metal. Check that all gas connections, both exterior 3 0.2 0.6
and interior to the system, are leak tight. 5 0.3 0.8
10 0.4 1.3
9.3 Verify that the ether/alcohol trap conditions satisfacto- 15 0.5 1.8
rily retain ethers. Analyze Set Up Mixture 1 or 2, depending on 20 0.6 2.2
25 0.7 2.6
whether samples contain MTBE or ETBE, using a method to 30 0.8 3.0
set the switching valves so that only the nonpolar column and 35 0.9 3.3
ether/alcohol trap are in the flow path. Determine the elution 40 1.0 3.7
45 1.1 4.0
time of the MTBE (or ETBE). The ether/alcohol trap condi- 50 1.2 4.3
tions are satisfactory if the ether peak begins to elute after 5.5
min and the peak shows a steep frontal portion. If the ether
peak begins to elute earlier or the frontal is not steep, decrease
the temperature of the ether/alcohol trap and reoptimize the 10. Procedure
system. 10.1 Sample Preparation—Because the ether/alcohol and
NOTE 7—If the oxygenate composition is unknown, the sample will
olefin traps have specific capacities that must not be exceeded,
require analysis by Test Method D4815, D5599, or other test methods. If some samples will need to be diluted to stay within the working
it is found that ETBE is present, only C4 through C9 olefins can be concentration range limits of the system.
determined. 10.1.1 Generally, the total olefin concentration must be
9.4 Optimize the olefin trap temperature by analyzing Cali- lower than 5 %. When relatively large amounts of C4 and C5
bration Standard 1 or 2 as described in 10.3, depending on olefins are present, a lower final concentration is required. In
whether samples contain MTBE or ETBE. A typical chromato- addition, the maximum total ether concentration is limited to
gram is shown in Fig. 2. Verify that undecane is completely 5 %. When any of these conditions is exceeded, a dilution of
eluted before 10 min while penetene is quantitatively (see Note the sample is required prior to analysis.
8) retained. If the undecane has a longer retention time, the 10.2 Samples are diluted using iso octane as a diluent. Fig.
olefin trap temperature must be increased. If pentene is not 3 is a Sample Dilution Decision Diagram that shows examples
being quantitatively retained, the olefin trap temperature must of dilutions that can be used to obtain appropriate dilution for
be decreased. Adjust the olefin trap temperature as necessary, specific samples. Other dilutions may be necessary depending
and reanalyze the calibration standard until the above condi- on the capacity of the olefin trap as determined by monitoring
tions are met. breakthrough (see Note 9) of olefins using the QC sample.
NOTE 8—As compared to the precision statement (see Table 5). Bring samples and calibration mixture to ambient temperature
prior to dilution during sample preparation.
9.5 Analyze the quality control sample, see 8.8. Verify that
results are consistent with those previously obtained and that NOTE 9—Breakthrough can be recognized in the chromatogram by the
C4 and C5 olefins are quantitatively (see Note 8) retained by the signal not returning to baseline within the first 10 min.
olefin trap. If C4 and C5 olefins are not quantitatively retained, 10.2.1 To prepare dilutions, tare to the nearest 0.1 mg, a
reoptimize the olefin trap temperature (see 9.4). glass container that can be sealed, preferably with a polyeth-
9.5.1 Reoptimize the system (see 9.1) whenever the QC ylene screw cap or equivalent, and that is large enough to
sample results do not conform to those expected. contain both the specimen and isooctane. Pipette a minimum of

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 D6296 − 98 (2008)

FIG. 3 Sample Dilution Decision Diagram

1 mL of sample into the container and reweigh. Pipette a 10.3 Sample Analysis—Load the necessary system set-point
sufficient volume of isooctane into the container to obtain the conditions, which include initial system component tempera-
desired dilution ratio. For example, if a 1:3 dilution is desired, tures, times at which column and trap temperatures are
pipette 5 mL of sample followed by 15 mL of isooctane. changed, the initial positions of switching valves, and times
Calculate a dilution factor: when valve switches occur (see Note 6).
V sam 10.4 When all component temperatures have stabilized at
D dil 5 (1)
V sam 1V dil the analysis conditions, inject a reproducible 0.2-µL aliquot of
a representative sample (or calibration test mixture), and start
where:
the analysis.
Ddil = dilution factor, 10.4.1 Starting the analysis should begin the timing function
Vsam = volume of sample added, mL, and
that controls all of the various programmed temperature
Vdil = volume of isooctane diluent, mL.
changes and valve switching. It should also initiate the acqui-
10.2.2 Calculate the density of the sample to three decimal sition of peak area integration data for the C4 to C10 olefin
places: peaks.
M 10.4.2 Upon completion of its programmed cycle, the sys-
D5 (2) tem should automatically stop, generate a chromatogram, and
V
print a report of total olefin concentration. A typical sample
where: chromatogram is shown in Fig. 4.
D = density, kg/L,
M = mass of sample pipetted, g, and NOTE 10—If results are to be calculated by the system computer, load
the dilution factor (if any) and the sample density, if mass % is to be
V = volume of sample pipetted, mL. calculated.

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 D6296 − 98 (2008)

FIG. 4 Typical Sample Chromatogram

11. Calibration verted to a volume-based response. To accomplish this conver-

11.1 Blank Compensation—Analyze a sample of pure isooc- sion, the density of the olefin fraction must be calculated. The
tane in duplicate and discard the first analysis. The blank signal computer software is able to perform this calculation using the
from the second analysis is recorded and stored by the software retention times of the C5 to C10 olefins as recorded in the
to be subtracted from the signal obtained for the olefins during calibration run and the known densities of the individual
the calibration or sample analysis. The blank must be analyzed blended olefins, which are similar to olefinic components in
immediately before, and every time, a calibration is run. samples. The density for area slices at specific retention times
(between carbon numbers) is calculated by using a linear
11.2 Calibration—Confirms that the chromatographic sepa- interpolation of adjacent densities. The integrated area of each
ration is performed as required, determines the retention times carbon number slice from the sample chromatogram is divided
of the olefins by carbon number, and determines the response by the appropriate density. The corrected areas are then
factor on the FID for the olefins. summed to produce a total area that is corrected for olefin
11.2.1 Analyze Calibration Standard 1 for all samples ex- density (see Note 11).
cept those that contain ETBE as described in 10.3. When
ETBE is present, analyze Calibration Standard 2. [Link] Calculate a response factor for the total olefins in
[Link] A typical chromatogram of Calibration Standard 1 volume %/area using Eq 4.
is shown in Fig. 2. Visually inspect the chromatogram obtained G vol
Rfvol 5 (4)
to verify that symmetrical peaks are obtained for all olefins, A cor
that undecane completely elutes before 10 min, and that no
where:
ether peak elutes immediately before pentene. From the re-
corded areas of the olefin peaks and the known concentrations Rfvol = response factor for total olefins, volume %/area,
in the blend, verify that the calculated concentration for the Gvol = concentration of the C6 through C9 olefins in the
individual olefin peaks is satisfactory (see Note 8). If any of the calibration standard (Standard 1 or 2), volume %,
above conditions is not met, reoptimize the system to confirm and
Acor = integrated area of the C6 through C9 olefin peaks in
that column/trap temperatures and cut times are correct.
the calibration blend corrected for density (see
NOTE 11—The recorded areas of the olefins are blank subtracted as 11.2.3).
described in 11.1.
11.2.2 Response Factor, mass %—Calculate a response 12. Calculation
factor for the total olefins in mass %/area, using Eq 3.
12.1 Examine the report carefully to ensure that peak areas
NOTE 12—Only the integrated areas of the C6 through C9 olefin peaks for the olefins have been properly integrated.
are used for calculation of the response factor.
12.2 Total Olefins, mass %—To obtain a mass-percent
G mass
Rfmass 5 (3) result, the injected volume of sample must be converted to the
A
injected mass of the sample. The density, which must be
where: determined (see Eq 2), on each analyzed sample is used for this
Rfmass = response factor for total olefins, mass %/area, conversion. The calculation of total olefins can be performed
Gmass = concentration of C6 through C9 olefins in the cali- by the software when the calibration standard density, sample
bration standard (Standard 1 or 2), mass %, and density, and dilution have been entered prior to sample
A = integrated area of the C6 through C9 olefin peaks in analysis, or the total olefins, mass %, can be calculated using
the calibration blend. Eq 5.
11.2.3 Response Factor, Volume %—To obtain a volume % Rfmass X Q X D std
O mass 5 (5)
result, the mass-based response of the olefins must be con- D samp X D dil

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 D6296 − 98 (2008)
where: 14.1.1 Repeatability—The difference between successive
Omass = total olefins, mass %, results obtained by the same operator with the same apparatus
Rfmass = response factor, previously defined, Eq 3, under constant operating conditions on identical test materials
Dstd = density of the calibration standard, kg/L, would, in the long run, in the normal and correct operation of
Dsamp = density of the sample, kg/L, previously calculated, the test method, exceed the repeatability values calculated by
Eq 2, the following equation only in one case in twenty (see Table 5).
Ddil = dilution factor for the sample, previously calcu-
lated, Eq 1, and Repeatability 5 0.074 3 X 0.72 (7)
Q = integrated area of the total olefins from the sample where X is the average of two results in volume %.
chromatogram.
14.1.2 Reproducibility—The difference between two single
12.3 Total Olefins, Volume %—The calculation of total and independent results obtained by different operators work-
olefins can be performed by the software when the dilution ing in different laboratories on identical test materials would, in
factor has been entered prior to sample analysis, or the total the long run, in the correct operation of the test method, exceed
olefins, volume %, can be calculated using Eq 6.
the values calculated by the following equation only in one
Rfvol X Q cor case in twenty (see Table 5).
O LV 5 (6)
D dil
Reproducibility 5 0.26 3 X 0.72 (8)
where:
OLV = total olefins, liquid-volume %, where X is the average of two results in volume %.
Rfvol = response factor, previously defined, Eq 4, 14.2 Bias—No information can be presented on the bias of
Qcor = integrated area of the total olefins from the sample the procedure in Test Method D6296for measuring total olefin
chromatogram corrected for density (see 11.2.3), and content because no material having an accepted reference value
is available.
Ddil = dilution factor for the sample, previously calculated,
Eq 1.
15. Keywords
13. Report 15.1 gas chromatography; gasoline; multidimensional gas
13.1 Report the volume % or mass %, or both, for the total chromatography; olefins; spark-ignition engine fuels
olefins to the nearest 0.1 %.
14. Precision and Bias
14.1 Precision—The precision6 of this test method as deter-
mined by the statistical examination of the interlaboratory test
results is as follows:

6
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