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
ponent concentrations and precision are determined in the may co-elute with the hydrocarbons. If determination of these
range of 0.01 to approximately 30 mass %. The procedure may specific compounds is required, it is recommended that test
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. 1.6 Annex A1 of this test method compares results of the
1.3 The test method also determines methanol, ethanol, 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 ignition engine interlaboratory cooperative study samples. Although benzene,
fuels in the concentration range of 1 to 30 mass %. However, toluene, and several oxygenates are determined, when doubtful
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.

1
 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.
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
computer. Each eluting component is identified by comparing retention time and areas of eluting peaks. The system shall be
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
tration of each component in mass % is determined by (R) is extremely useful as it will replace the need to carry out
normalization of the peak areas after correction of selected the manual calculations which must be performed as listed in
components with detector response factors. The unknown 8.3.
components are reported individually and as a summary total. 6.4.1 Electronic Integrators, shall be capable of storing up
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

FIG. 1 Chromatogram for Reference Spiked Gasoline

3
 D 6729

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

FIG. 1 Chromatogram for Reference Spiked Gasoline (continued)

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

FIG. 1 Chromatogram for Reference Spiked Gasoline (continued)

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

6
 D 6729

FIG. 1 Chromatogram for Reference Spiked Gasoline (continued)

7
 D 6729

FIG. 1 Chromatogram for Reference Spiked Gasoline (continued)

8
 D 6729

FIG. 1 Chromatogram for Reference Spiked Gasoline (continued)

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.

9
 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
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).

TABLE 1 Chromatographic Operating Conditions, Column Requirements and Data Acquisition Requirements
Chromatographic Conditions Requirements
Injector settings
Injector temperature, °C 250
Split ratio 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 temperature, °C 130
Final time, min 0
3rd ramp rate, °C/min 4
Final temperature, °C 270
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.

10
 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 F log ~Ti! – log ~Tn!
log ~TN! – log ~Tn! G (5)

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.
the sample vials. The sample aliquot container, or the vial, or 10.3 Determine the hydrocarbon response factors by using
both, can also be cooled prior to the transfer of the original 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-
ommended that they be kept away from direct heat or light. No where:
other sample preparations are necessary for samples stored in 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,
manufacturer’s instructions. Nc = number of carbon atoms in the molecule, and
9.5 It is recommended that a quality assurance (QA) sample MWCH4 = 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. Aci 5 ~A!I ~RRF!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
 D 6729
TABLE 5 Response Factors of Oxygenated Compounds
Relative Response Factors
Analytes
RRF C7= 1.000 RRF CH4= 1.000
Methanol 2.996 2.672
Ethanol 2.087 1.862
t-Butanol (TBA) 1.302 1.161
Methyl-t-butyl ether (MTBE) 1.577 1.407
Ethyl-t-butyl ether (ETBE) 1.407 1.255
t-Amyl methyl ether (TAME) 1.356 1.210

where: able software may be used to provide this function, as well as

(Ac)i = corrected area, the calculation of other properties of petroleum liquids.
Ai = acquired area for an individual component, and
RRF = relative response factor (weight basis). 13. Precision and Bias 8
10.4.1 The percent weight (% W) is calculated as follows: 13.1 The repeatability and reproducibility precision esti-
~AC!i
mates are quoted in Annex A1.
% Wi 5 i 5 n 3 100 (8) 13.2 Precision Statement Outline—(> Analyte Qualification
( Aci
i51
Process):
13.2.1 For each analyte to qualify for a precision statement,
where: it must be present in at least six samples, and detected by at
%W = percent weight of the component i in the least six laboratories, at least once, in accordance with RR:
mixture, and D02-1007 requirements.
i5n = summation of all the corrected areas for 13.2.2 The (repeatability standard deviation)/mean value for
(
i51
Aci the components analyzed. each analyte/sample combination must be less than or equal to
0.1, in accordance with LOQ requirements which, while not a
10.4.1.1 The subscript i indicates that the operations are standard, is what CS94 is recommending.
carried out for each individual component in the matrix. 13.3 A brief explanation of headers in Table A1.2 follows:
10.5 In the case of unidentified components, utilize a 13.3.1 ID: self explanatory,
relative response factor of 0.800 (relative to methane). 13.3.2 rmin: lower 95 % confidence limit of rest,
13.3.3 rest: repeatability estimate in percentage of concen-
11. Oxygenates tration,
11.1 A cooperative study for linearity was performed for 13.3.4 rmax: upper 95 % confidence limit of rest,
methanol, ethanol, t-butanol, methyl-t-butyl ether (MTBE), 13.3.5 Rmin, Rest, Rmax: same as above except for reproduc-
ethyl-t-butyl ether (ETBE), and t-amyl methyl ether (TAME) in ibility,
concentration ranges from 1.0 mass % up to 30 mass % (Annex 13.3.6 Cmin: lower concentration limit that rest, Rest is
A2). The average relative response factors for the oxygenates applicable, and
were calculated from the study and are listed in Table A2.1. 13.3.7 Cmax: upper concentration limit that rest, Rest is
They have been incorporated into the IHA Method. The applicable.
percent standard deviation of these relative response values 13.4 The summaries for the paraffins, isoparaffins, C2 ben-
was as high as 7 %. MTBE was the only oxygenate that was zene, and oxygenates follow the same procedure that was used
present in sufficient number of samples to meet the ASTM for the analytes and are listed in Table A1.3.
requirements for round robin testing in accordance with RR: 13.5 Bias—The bias of this test method cannot be deter-
D02-1007. Therefore the statistical data for MTBE should be mined since an appropriate standard reference material is not
taken from Table A1.2. available.

12. Expression of Results 14. Keywords

12.1 Report the concentration of each components as mass 14.1 gas chromatograph; gasoline; individual hydrocarbon
% (m/m) to the nearest 0.001 %. analysis; oxygenated fuels; spark-ignition engine fuels
12.2 The data for individual components may by grouped
by summing the concentration of compounds in each particular 8
Supporting data describing the interlaboratory cooperative study to determine
group type such as paraffin, isoparaffin, olefin, aromatic, precision and bias has been filed at ASTM International Headquarters and may be
naphthene, oxygenates, and unknowns. Commercially avail- obtained by requesting RR: D02-1519.

12
 D 6729
ANNEXES

(Mandatory Information)

A1. HYDROCARBON DATA

A1.1 Table A1.1 presents the component retention times A1.4 The precision statement for the olefins and cyclopar-
and properties. affins is determined by taking the square root of the value
determined in the summary; multiply by the coefficient (rcoef)
A1.2 Table A1.2 represents the repeatability and reproduc- for repeatability and the coefficient (Rcoef) for the reproduc-
ibility precision estimates prepared by statisticians of CS94 in
ibility.
accordance with RR: D02-1007. The analyte qualification
Name rmin rcoef rmax Rmin Rcoef Rmax Cmin Cmax
process for precision statements is outlined as follows: Cycloparaffins 0.0726 0.08 0.098 0.286 0.384 0.586 2 10
A1.2.1 For each analyte to qualify for a precision statement, Olefins 0.1555 0.18 0.21 0.382 0.555 1.012 2 25
it must be present in at least six samples, and detected by at
least six laboratories, at least once, in accordance with RR: A1.5 The precision for the aromatics does not depend on
D02-1007 requirements. level and is stated below in weight %.
A1.2.2 The (repeatability standard deviation)/mean value Name rmin r% rmax Rmin R% Rmax Cmin Cmax
Aromatics 0.8549 0.98 1.155 2.151 2.706 3.651 15 50
for each analyte/sample combination must be less than or equal
to 0.1, in accordance with LOQ requirements which, while not
A1.6 The summaries for the paraffins, isoparaffins,
a standard, is what CS94 is recommending.
C2benzene and oxygenates follow the same procedure that was
A1.3 Summary for Oxygenates: Warning—The statistical used for the analytes. The statistics for the grouping are shown
data could be done on the oxygenates but there was not an in Table A1.3 as an indication of reproducibility and repeat-
equal number of all oxygenates in the round robin. MTBE was ability of reporting the results as a group summary. However,
the largest contributor to the statistical results. The number of there is a possibility that significant error could occur due to
samples that contained each oxygenate is as follows: co-elution of peaks, the presence of significant amounts of
Oxygenate No. of Approximate olefinic or naphthenic constituents, or both, above octane and
Type Samples Concentration Range
Ethanol 2 1 %, and 12 %
the percent unknown in the sample. If more accurate summary
t-butanol 2 .20 %, and 1.0 % results are needed that are not covered by the above precision
MTBE 6 1, 2, 4, 4, 8 and 16 % statement, for some or all of the above families of components,
ETBE 1 0.50 %
TAME 1 15.00 % please consider another ASTM test method.

TABLE A1.1 Component Retention Times and Properties

NOTE 1—The names used are from several other tables and changes have been made where the GCMS did not agree with the peak name or its retention
time.
NOTE 2—n-propanol will coelute with 3M-1-C5=.
NOTE 3—MTBE will coelute with 23DN-1C4=.
NOTE 4—MSBE will coelute with 1-hexene.
NOTE 5—ETBE will coelute with 23DM-13C4= =.
NOTE 6—isobutanol will coelute with 44DM-1-c5=.
NOTE 7—233TM pentane will coelute with toluene when the ratio with toluene is greater than 5.0:1.
NOTE 8—The coeluting olefins in Notes 2-6 will usually be below 1000 ppm.
NOTE 9—In some instances the chemical group is known, but the chemical structure is not known (for example, C6-olefin; the position of the double
bond is not known).
NOTE 10—Relative response factors for six of the major oxygenated compounds have been determined by using the average results from seven
laboratories analyzing six samples in duplicate. These same samples were used to determine linearity of methanol, ethanol, t-butanol, MTBE, ETBE and
TAME from a concentration level ranging from 1 mass % up to 30 mass %.

Peak No. New Name Retention Time Molecular Mass, MWt Theoretical Mass, Rf, (C1)
1 Methane 6.74 16.04 1.000
2 Ethene 7.10 28.05 0.874
3 Ethane 7.21 30.07 0.937
4 Propene 7.41 42.05 0.874
5 Propane 7.87 44.11 0.916
6 Isobutane 8.26 58.12 0.906
7 Methanol 8.64 32.03 2.672
8 Isobutene 8.95 56.11 0.874
9 1-butene 8.99 56.11 0.874
10 1,3-butadiene 9.17 54.09 0.843
12 N-butane 9.28 58.12 0.906
14 Trans-2-butene 9.70 56.11 0.874

13
 D 6729

TABLE A1.1 Continued

Peak No. New Name Retention Time Molecular Mass, MWt Theoretical Mass, Rf, (C1)
16 2,2-dimethylpropane 9.82 72.15 0.899
18 Cis-2-butene 10.33 56.11 0.874
20 1,2-butadiene 10.88 54.09 0.843
22 Ethanol 11.39 46.07 1.862
24 3-methyl-1-butene 12.21 70.13 0.874
26 Isopentane 13.57 72.15 0.899
28 1,4-pentadiene 14.25 68.12 0.849
30 2-Butyne (dimethylacetylene) 14.57 54.09 0.843
32 1-pentene 15.03 70.13 0.874
34 Isopropanol 15.28 60.11 1.950
36 2-methyl-1-butene 15.76 70.13 0.874
38 N-pentane 16.24 72.15 0.899
40 2-methyl-1,3-butadiene 16.73 68.12 0.849
42 Trans-2-pentene 17.23 70.13 0.874
44 3,3-dimethyl-1-butene 17.86 84.16 0.874
46 Cis-2-pentene 18.17 70.13 0.874
48 Tert-butanol (TBA) 18.51 74.12 1.161
50 2-methyl-2-butene 18.76 70.13 0.874
52 Trans-1,3-pentadiene 19.12 68.12 0.849
54 3-methyl-1,2-butadiene 19.48 68.12 0.849
56 Cyclopentadiene 19.76 67.10 0.824
58 Cis-1,3-pentadiene 20.25 68.12 0.849
60 1,2-pentadiene 20.51 68.12 0.849
62 2,2-dimethylbutane 20.69 86.18 0.895
64 Cyclopentene 23.16 68.12 0.849
66 4-methyl-1-pentene 24.30 84.16 0.874
68 3-methyl-1-pentene 24.38 84.16 0.874
70 n-propanol 24.68 60.11 1.770
72 Cyclopentane 24.86 70.13 0.874
74 2,3-dimethylbutane 25.57 86.18 0.895
76 2,3-dimethyl-1-butene 25.99 84.16 0.874
78 Methyl tert-butyl ether (MTBE) 26.18 88.09 1.407
80 Cis-4-methyl-2-pentene 26.48 84.16 0.874
82 2-methylpentane 26.66 86.18 0.895
84 Trans-4-methyl-2-pentene 72.09 84.16 0.874
86 Methyl ethyl ketone (MEK) 28.00 72.06 1.570
88 3-methylpentane 29.15 86.18 0.895
90 C6-olefin 29.61 84.16 0.874
92 2-methyl-1-pentene 30.29 84.16 0.874
94 1-hexene 30.52 84.16 0.874
96 Methyl sec-butyl ether (MSBE) 30.66 88.09 1.550
98 C6-olefin 30.94 84.16 0.874
100 2-butanol 31.56 74.12 1.600
102 2ethyl-1-butene 32.47 84.16 0.874
104 N-hexane 32.75 86.18 0.895
106 Cis-3-hexene 33.41 84.16 0.874
108 Di-isopropyl ether (DIPE) 33.58 102.00 1.600
110 Trans-3-hexene+hexadiene 33.86 84.16 0.874
112 2-methyl-2-pentene 34.33 84.16 0.874
114 3-methylcyclopentene 34.57 82.10 0.853
116 Trans-3-methyl-2-pentene 34.71 84.16 0.874
118 Cis-2-hexene 35.62 84.16 0.874
120 3,3-dimethyl-1-pentene 36.04 98.19 0.874
122 Cis-3-methyl-2-pentene 36.92 84.16 0.874
124 Ethyl tert-butyl ether (ETBE) 37.07 102.18 1.255
126 2,3-dimethyl-1,3-butadiene 37.19 82.10 0.853
128 Methylcyclopentane 37.40 84.16 0.874
130 2,2-dimethylpentane 37.60 100.21 0.892
132 4,4-dimethyl-1-pentene 37.91 98.19 0.874
134 Isobutanol 38.06 74.12 1.500
136 2,3-dimethyl-2-butene 38.30 84.16 0.874
138 2,4-dimethylpentane 38.99 100.21 0.892
140 1,3,5-hexatriene 39.31 80.06 0.832
142 2,2,3-trimethylbutane 39.48 100.21 0.892
144 Methylcyclopentadiene 40.17 80.06 0.832
146 C7-olefin 40.30 98.19 0.874
148 C7-olefin 40.68 98.19 0.874
150 C7-diolefin 41.20 96.18 0.856
152 4-methylcyclopentene 41.44 82.10 0.853
154 Methylenecyclopentane 42.08 82.10 0.853
156 Benzene 42.30 78.05 0.812
158 1-methyl-1-cyclopentene 42.46 82.10 0.853
160 C7-olefin 43.06 98.19 0.874
162 C2-methyl-3-hexene 43.37 98.19 0.874

14
 D 6729

TABLE A1.1 Continued

Peak No. New Name Retention Time Molecular Mass, MWt Theoretical Mass, Rf, (C1)
164 3,3-dimethylpentane+5-methyl-1- 43.81 100.21 0.892
hexene
166 Cyclohexane 44.07 84.16 0.874
168 Trans-2methyl-3-hexene 44.82 98.19 0.874
170 3,3-dimethyl-1,4-pentadiene 45.44 96.18 0.856
172 N-butanol 45.58 74.12 1.500
174 Dimethylcyclopentadiene 45.69 94.17 0.838
176 t,2-ethyl-3-methyl-1-butene 45.97 98.19 0.874
178 4-methyl-1-hexene 46.27 98.19 0.874
180 C7-olefin 46.55 98.19 0.874
182 3-methyl-1-hexene 46.78 98.19 0.874
184 4-methyl-2-hexene 46.92 98.19 0.874
186 2-methylhexane+C7-olefin 47.29 100.21 0.892
188 2,3-dimethylpentane 47.51 100.21 0.892
190 Cyclohexene 47.65 82.10 0.853
192 Tert-amyl methyl ether (TAME) 48.10 102.18 1.210
194 C7-olefin 48.46 98.19 0.874
196 C7-olefin 48.64 98.19 0.874
198 3-methylhexane 49.05 100.21 0.892
200 C7-olefin 49.47 98.19 0.874
202 C7-olefin 49.62 98.19 0.874
204 Trans-1,3-dimethylcyclopentane 49.83 98.19 0.874
206 Cis-1,3-dimethylcyclopentane 50.40 98.19 0.874
208 Trans-1,2-dimethylcyclopentane 51.01 98.19 0.874
210 3-ethylpentane 51.21 100.10 0.892
212 C7-olefin 51.43 98.19 0.874
214 2,2,4-trimethylpentane 51.61 114.23 0.890
216 C7-olefin 51.75 98.19 0.874
218 1-heptene 52.05 98.19 0.874
220 C7-olefin 52.18 98.19 0.874
222 2,3-dimethyl-1,3-pentadiene 52.69 96.18 0.874
224 C7-diolefin 53.00 96.18 0.856
226 C7-olefin 53.36 98.19 0.874
228 C7-diolefin 53.81 96.18 0.856
230 C7-diolefin 54.13 96.18 0.856
232 C7-olefin 54.28 98.19 0.874
234 N-heptane 54.59 100.21 0.892
236 Cis-3-heptene 54.81 98.19 0.874
238 2-methyl-2-hexene 55.10 98.19 0.874
240 Cis-methyl-3-hexene 55.35 98.19 0.874
242 Trans-3-heptene 55.72 98.19 0.874
244 3-ethyl-2-pentene 55.88 96.18 0.856
246 1,5-dimethylcyclopentene 56.06 96.18 0.856
248 Trans-2-methyl-3-hexene 56.58 98.19 0.874
250 C7-diolefin+C7-triolefin 57.01 96.18 0.856
252 2,3-dimethyl-2-pentene 57.35 98.19 0.874
254 3-ethylpentene 57.57 98.19 0.874
256 Methylcyclohexane 57.79 98.19 0.874
258 C7-olefin 58.28 98.19 0.874
260 1,1,3-trimethylcyclopentane 58.79 112.22 0.874
262 2,2-dimethylhexane 59.29 114.10 0.890
264 2,3,4-trimethyl-1,4-pentadiene 59.45 110.21 0.859
266 3,3-dimethyl-1,5-hexadiene 59.79 110.21 0.859
268 C8-olefin 60.12 98.19 0.874
270 Ethylcyclopentane 60.60 98.19 0.874
272 3-methylcyclohexene 60.99 96.18 0.856
274 Methylcyclohexadiene 61.14 94.17 0.838
276 2,2,3-trimethylpentane 61.22 114.10 0.890
278 2,5-dimethylhexane+C8-olefin 61.59 114.23 0.890
280 2,4-dimethylhexane 61.91 114.23 0.890
282 C7-triolefin+C8-olefin 62.28 96.18 0.856
284 Trans,cis-1,2,4- 62.68 112.22 0.874
trimethylcyclopentane
286 3,3-dimethylhexane+C8-olefin 63.13 114.23 0.890
288 C7-triolefin+C8-olefin 63.39 96.18 0.856
290 C8-olefin 63.69 112.22 0.874
292 Trans,cis-1,2,3- 64.27 112.22 0.874
trimethylcyclopentane
294 C8-olefin 64.52 112.22 0.874
296 C8-olefin 64.73 112.22 0.874
298 C8-olefin 64.82 112.22 0.874
300 2,3,4-trimethylpentane 64.94 114.23 0.890
302 C7-diolefin 65.25 96.18 0.856
304 Toluene 65.50 92.06 0.821

15
 D 6729

TABLE A1.1 Continued

Peak No. New Name Retention Time Molecular Mass, MWt Theoretical Mass, Rf, (C1)
306 2,3,3-trimethylpentane 65.76 114.23 0.890
308 C8-olefin 65.90 112.22 0.874
310 C8-diolefin 66.12 110.21 0.859
312 C8-olefin 66.48 112.22 0.874
314 C8-olefin 66.65 112.22 0.874
316 C8-olefin 67.08 112.22 0.874
318 C8-diolefin+C8-olefin 67.30 110.21 0.859
320 2,3-dimethylhexane 67.47 114.23 0.890
322 2-methyl-3-ethylpentane 67.71 114.23 0.890
324 1,1,2-trimethylcyclopentane+C7- 68.04 112.22 0.874
triolefin
326 C8-diolefin+C8-paraffin 68.31 110.21 0.859
328 C8-olefin 68.41 112.22 0.874
330 C8-olefin 68.64 112.22 0.874
332 2-methylheptane 68.86 114.23 0.890
334 4-methylheptane 69.11 114.23 0.890
336 C8-diolefin+C7-olefin 69.41 112.22 0.874
338 C8-olefin 69.70 112.22 0.874
340 Cis-1,3-dimethylcyclohexane 69.91 112.22 0.874
342 Trans-1,4-dimethylcyclohexane 70.01 112.22 0.874
344 3-methylheptane 70.23 114.23 0.890
346 3-ethylhexane 70.38 114.23 0.890
348 C8-diolefin 70.51 110.21 0.874
350 C8-olefin 70.72 112.22 0.874
352 C8-olefin 70.92 112.22 0.874
354 1,1-dimethylcyclohexane 71.18 112.22 0.874
356 C8-olefin 71.43 112.22 0.874
358 C8-olefin 71.70 112.22 0.874
360 Cis-1-ethyl-3-methylcyclopentane 72.10 112.22 0.874
362 2,2,5-trimethylhexane 72.23 128.26 0.888
364 Trans-1-ethyl-3- 72.46 112.22 0.874
methylcyclopentane
366 Trans-1-ethyl-2- 72.68 112.22 0.874
methylcyclopentane
368 1-methyl-1-ethylcyclopentane 72.96 112.22 0.874
370 1-octene 73.16 112.22 0.874
372 C8-olefin 73.26 112.22 0.874
374 Trans-1,2-dimethylcyclohexane 73.36 112.22 0.874
376 C8-olefin 73.48 112.22 0.874
378 C8-olefin 73.68 112.22 0.874
380 Trans-3-C8-Olefin 74.08 112.11 0.874
382 C8-olefins 74.45 112.22 0.874
384 Trans-1,3-dmcyclohexane 74.66 112.22 0.874
386 Cis-1,4-dmcycloHexane 74.79 112.22 0.874
388 N-octane 74.98 114.23 0.890
390 C8-olefin 75.33 112.22 0.874
392 C8-olefin 75.49 112.22 0.874
394 Trans-2-octene 75.62 112.22 0.874
396 Isopropylcyclopentane 75.72 112.22 0.874
398 C9-olefin 75.85 126.24 0.874
400 C9-olefin 75.89 126.24 0.874
402 C9-olefin 75.90 126.24 0.874
404 C9-olefin 76.08 126.24 0.874
406 2,2,4-trimethylhexane 76.31 128.26 0.888
408 2,4,4-trimethylhexane 76.62 128.26 0.888
410 C9-olefins 76.86 126.24 0.874
412 2,3,5-trimethylhexane 77.29 128.26 0.888
414 Cis-2-octene 77.53 112.22 0.874
416 2,2,3,4-tetramethylpentane 77.77 128.26 0.888
418 2,2-dimethylheptane 78.02 128.26 0.888
420 Cis-1,2-dimethylcyclohexane 78.36 112.22 0.874
422 2,4-dimethylheptane 78.74 128.26 0.888
424 C9-olefin 78.90 126.24 0.874
426 C9-olefin 79.08 126.24 0.874
428 Ethylcyclohexane 79.24 112.22 0.874
430 Propylcyclopentane 79.39 112.22 0.874
432 2-methyl-4-ethylhexane 79.59 128.26 0.888
434 2,6-dimethylheptane 79.74 128.26 0.874
436 C9-olefin 79.85 126.24 0.874
438 1,1,4-trimethylcyclohexane 80.05 126.24 0.874
440 C9-olefin 80.28 126.24 0.874
442 C9-olefin 80.38 126.24 0.874
444 1,1,3-trimethylcyclohexane 80.52 126.24 0.874
446 2,5 & 3,5-dimethylheptane 80.69 128.26 0.888

16
 D 6729

TABLE A1.1 Continued

Peak No. New Name Retention Time Molecular Mass, MWt Theoretical Mass, Rf, (C1)
448 C9-olefin 80.88 126.24 0.874
450 3,3-DMheptane 81.00 128.26 0.888
452 C9-paraffin 81.13 128.26 0.888
454 C9-olefin 81.34 126.24 0.874
456 2,3,3-trimethylhexane 81.56 128.26 0.888
458 C9-olefin 81.68 126.24 0.874
460 Ethylbenzene 81.96 106.08 0.827
462 C9-olefin 82.00 126.24 0.874
464 Trans-1,2,4-trimethylcyclohexane 82.31 126.24 0.874
466 C9-olefin 82.33 126.24 0.874
468 2,3,4-trimethylhexane 82.63 128.26 0.888
470 C9-olefin 82.73 126.24 0.874
472 3,3,4-trimethylhexane 82.89 128.26 0.888
474 M-Xylene 83.30 106.08 0.827
476 P-Xylene 83.43 106.08 0.827
478 2,3-dimethyheptane 83.57 128.26 0.888
480 3,5-dimethylheptane 83.83 128.26 0.888
482 3,4-dimethylheptane 83.91 128.26 0.888
484 C9-olefin 84.08 126.24 0.874
486 3-methyl-3-ethylhexane 84.26 128.26 0.888
488 C9-olefin 84.41 126.24 0.874
490 4-ethylheptane 84.52 128.26 0.888
492 4-methyloctane+C9-olefin 84.70 128.26 0.888
494 2-methyloctane 84.84 128.26 0.888
496 C9-olefin 85.01 126.24 0.874
498 C9-paraffin 85.18 128.26 0.888
500 C9-olefin 85.36 126.24 0.874
502 3-ethylheptane 85.51 128.26 0.888
504 3-methyloctane 85.69 128.26 0.888
506 C9-paraffin 85.87 126.24 0.874
508 Cis-1,2,4-trimethylcyclohexane 85.91 126.24 0.874
510 1,1,2-trimethylcyclohexane 86.05 126.24 0.874
512 O-Xylene 86.27 106.08 0.827
514 C9-olefin 86.47 126.24 0.874
516 C9-paraffin 86.57 128.26 0.888
518 C9-paraffin 86.75 128.26 0.888
520 C9-olefin 86.90 126.24 0.874
522 Trans-1-ethyl-4- 87.08 126.24 0.874
methylcyclohexane
524 Cis-1-ethyl-4-methylcyclohexane 87.23 126.24 0.874
526 C9-paraffin 87.49 128.26 0.888
528 1-nonene 87.79 126.24 0.874
530 Isobutylcyclopentane 88.00 126.24 0.874
532 C9-paraffin 88.45 128.26 0.888
534 Trans-3-nonene 88.65 126.24 0.874
536 Cis-3-nonene 88.82 126.24 0.874
538 C9-paraffin 89.09 128.26 0.888
540 n-nonane 89.24 128.26 0.888
542 C10-olefin 89.41 140.27 0.874
544 Trans-2-nonene 89.74 126.24 0.874
546 1-methyl-1-ethylcyclohexane 89.61 126.24 0.874
548 1-methyl-2-propylcyclopentane 89.96 126.24 0.874
550 C10-olefin 90.09 140.27 0.874
552 C10-paraffin 90.18 142.28 0.887
554 C10-paraffin 90.29 142.28 0.887
556 Isopropylbenzene 90.46 118.08 0.832
558 Cis-2-nonene 90.78 126.24 0.874
560 Tert-butylcyclopentane 90.80 126.24 0.874
562 C9-olefins 90.88 126.24 0.874
564 Nonene 91.16 126.24 0.874
566 Isopropylcyclohexane 91.32 126.24 0.874
568 3,3,5-trimethylheptane 91.44 142.28 0.887
570 2,2-dimethyloctane 91.60 142.28 0.887
572 2,4-dimethyloctane 91.67 142.28 0.887
574 1-methyl-4-isopropylcyclohexane 91.82 140.27 0.874
576 Sec-butylcyclopentane 92.20 126.24 0.874
578 Propylcyclohexane 92.40 126.24 0.874
580 2,5-dimethyloctane 92.59 142.28 0.887
582 Butylcyclopentane 92.89 126.24 0.874
584 2,6-dimethyloctane 93.04 142.28 0.887
586 3,6-dimethyloctane 93.43 142.28 0.887
588 1-methyl-2-ethylcyclohexane 93.59 126.24 0.874
590 C10-olefin 93.79 140.27 0.874
592 Propylbenzene 93.96 120.20 0.832

17
 D 6729

TABLE A1.1 Continued

Peak No. New Name Retention Time Molecular Mass, MWt Theoretical Mass, Rf, (C1)
594 3,3-dimethyloctane 94.27 142.28 0.887
596 3-methyl-5-ethylheptane 94.54 142.28 0.887
598 C10-olefin 94.66 140.27 0.874
600 1-ethyl-3-methylbenzene 94.88 120.20 0.832
602 1-ethyl-4-methylbenzene 95.09 120.20 0.832
604 Naphthene 95.30 140.27 0.874
606 1,3,5-trimethylbenzene 95.73 120.20 0.832
608 2,3-dimethyloctane 95.94 142.28 0.887
610 5-methylnonane 96.13 142.28 0.887
612 4-methylnonane 96.29 142.28 0.887
614 2-methylnonane 96.49 142.28 0.887
616 1-ethyl-2-methylbenzene 96.77 120.20 0.832
618 3-ethyloctane 97.01 142.28 0.887
620 Naphthene 97.14 140.27 0.874
622 3-methylnonane 97.47 142.28 0.887
624 C10-olefin 97.69 140.27 0.874
626 C10-paraffin 97.83 142.28 0.887
628 C10-paraffin 98.16 142.28 0.887
630 1,2,4-trimethylbenzene 98.49 120.20 0.832
632 C10-paraffin 98.74 142.28 0.997
634 C10-paraffin 98.90 142.28 0.887
636 Isobutylcyclohexane 99.10 140.27 0.874
638 C10-paraffin 99.09 142.28 0.887
640 C10-paraffin 99.22 142.37 0.887
642 1-decene 99.52 140.27 0.874
644 C10-paraffin 99.66 142.28 0.887
646 C10-paraffin 99.70 142.28 0.887
648 C10-aromatic 99.75 134.22 0.837
650 C10-paraffin 99.82 142.28 0.887
652 Naphthene 99.93 140.27 0.874
654 Isobutylbenzene 100.06 134.22 0.837
656 Trans-1-methyl-2- 100.09 140.27 0.874
propylcyclohexane
658 C10-paraffin 100.19 142.28 0.887
660 Sec-butylbenzene 100.28 134.22 0.837
662 n-decane 100.40 142.28 0.887
664 C11-paraffin 100.67 156.32 0.886
666 C11-paraffin 100.85 156.32 0.886
668 1,2,3-trimethylbenzene 101.28 120.20 0.832
670 1-methyl-3-isopropylbenzene 101.40 134.22 0.837
672 C11-paraffin 101.55 156.32 0.886
674 1-methyl-4-isopropylbenzene 101.73 134.22 0.837
676 C11-paraffin 102.06 156.32 0.886
678 C11-paraffin 102.05 156.32 0.886
680 2,3-dihydroindene 102.42 118.17 0.819
682 Sec-butylcyclohexane 102.57 140.27 0.874
684 C11-paraffin 102.87 156.32 0.886
686 1-methyl-2-isopropylbenzene 103.03 134.22 0.837
688 3-ethylnonane 103.26 156.32 0.886
690 C11-paraffin 103.37 156.32 0.886
692 Naphthene 103.55 140.27 0.874
694 C11-paraffin 103.88 126.19 0.886
696 1,3-diethylbenzene 104.08 134.22 0.837
698 1-methyl-3-propylbenzene 104.35 134.22 0.837
700 1,4-diethylbenzene 104.57 134.22 0.837
702 1-methyl-4-propylbenzene 104.73 134.22 0.837
704 Butylbenzene 104.85 134.22 0.837
706 3,5-dimethyl-1-ethylbenzene 105.00 134.22 0.837
708 1,2-diethylbenzene 105.26 134.22 0.837
710 C11-paraffin 105.39 156.32 0.886
712 C10-aromatic 105.49 134.22 0.837
714 C10-aromatic 105.64 134.22 0.837
716 C10-aromatic 105.75 134.22 0.837
718 1-methy-2-propylbenzenes 105.85 134.22 0.837
720 C10-aromatic 105.95 134.22 0.837
722 5-methyldecane 106.11 156.32 0.886
724 4-methyldecane 106.26 156.32 0.886
726 2-methyldecane 106.39 156.32 0.886
728 C11-paraffin 106.55 156.32 0.886
730 1,4-dimethyl-2-ethylbenzene 106.76 134.22 0.837
732 1,3-dimethyl-4-ethylbenzene 106.93 134.22 0.837
734 C11-paraffin 107.06 156.32 0.886
736 3-methyldecane 107.27 156.32 0.886
738 C1- indane 107.35 132.00 0.837

18
 D 6729

TABLE A1.1 Continued

Peak No. New Name Retention Time Molecular Mass, MWt Theoretical Mass, Rf, (C1)
740 1,2-dimethyl-4-ethylbenzene 107.46 134.22 0.837
742 C11-paraffin 107.76 156.32 0.886
744 1,3-dimethyl-2-ethylbenzene 108.01 134.22 0.837
746 C11-paraffin 108.58 156.32 0.886
748 C11-paraffin 108.75 156.32 0.886
750 1-methyl-4-tert-butylbenzene 108.98 148.25 0.840
752 1,2-dimethyl-3-ethylbenzene 109.17 134.22 0.837
754 1-ethyl-2-isopropylbenzene 109.50 148.25 0.840
756 N-undecane 109.62 156.32 0.886
758 1-ethyl-4-isopropylbenzene 109.80 148.25 0.840
760 C12-paraffin 109.96 170.34 0.885
762 1,2,4,5-tetramethylbenzene 110.15 134.22 0.837
764 2-methylbutylbenzene 110.55 148.25 0.840
766 1,2,3,5-tetramethylbenzene 110.43 134.22 0.837
768 3 methylbutylbenzene 110.64 148.25 0.840
770 C11-aromatic 110.74 148.25 0.840
772 C12-paraffin 110.84 170.34 0.885
774 C11-aromatic 110.94 148.25 0.840
776 C11-aromatic 111.05 148.25 0.840
778 C11-aromatic 111.12 148.25 0.840
780 1-tert-butyl-2-methylbenzene 111.56 148.25 0.840
782 C11-aromatic 111.65 148.25 0.840
784 1-ethyl-2-propylbenzene 111.76 148.25 0.840
786 C11-aromatic 112.00 148.25 0.840
788 C11-aromatic 112.22 148.25 0.840
790 C11-aromatic 112.34 148.25 0.840
792 1-methyl-3-butylbenzene 112.52 148.25 0.840
794 C11-aromatic 112.63 148.25 0.840
796 1,2,3,4-tetramethylbenzene 112.79 148.25 0.840
798 Pentylbenzene 113.17 148.25 0.840
800 Trans-1-methyl-2- 113.44 168.33 0.874
(4methylpentyl)-cyclopentane
802 C11-aromatic 113.74 148.25 0.840
804 C11-aromatic 113.85 148.25 0.840
806 C11-aromatic 114.02 148.25 0.840
808 C12-paraffin 114.12 170.34 0.885
810 1,2,3,4-tetrahydronaphthalene 114.17 132.09 0.824
812 1-tert-butyl-3,5-dimethylbenzene 114.32 162.30 0.843
814 Naphthalene 114.65 128.06 0.799
816 1,1-dimethylindane 114.94 146.10 0.829
818 1,2-dimethylindane 115.19 146.10 0.829
820 1,6-dimethylindane 115.33 146.10 0.829
822 C11-aromatic 115.55 148.25 0.885
824 1- ethylindane 115.65 146.10 0.829
826 2- ethylindane 115.88 146.10 0.829
828 Ethyl -1,3,5-trimethylbenzene 116.00 148.25 0.884
830 1,3-dipropylbenzene 116.21 162.34 0.843
832 n-dodecane 116.55 170.34 0.885
834 Ethyl -1,2,4-trimethylbenzene 116.69 148.25 0.840
836 C11-aromatic 117.07 148.25 0.840
838 C11-aromatic 117.19 148.25 0.840
840 C12-aromatic+C2-indane 117.55 162.30 0.843
842 2,4-dimethylindane 117.99 146.10 0.829
844 4-ethylindane 118.13 146.10 0.829
846 1-tert-butyl-4-ethylbenzene 118.59 162.30 0.843
848 1,3-dimethylindane 119.07 146.10 0.829
850 1-methyl-4-pentylbenzene 119.60 162.30 0.843
852 4,7-dimethylindane 119.65 146.10 0.829
854 5,6-dimethylindane 119.70 146.10 0.829
856 C12-aromatic 119.77 162.30 0.843
858 Hexylbenzene 119.87 162.30 0.843
860 C6-benzene 119.93 162.30 0.843
862 C6-benzene 119.98 162.30 0.843
864 C6-benzene 120.20 162.30 0.843
866 4,5-dimethylindane 120.30 146.10 0.829
868 C6-benzene 120.80 163.30 0.843
870 2-methylnaphthalene 121.42 142.08 0.806
872 C6-benzene 121.65 162.30 0.843
874 C6-benzene 121.85 162.30 0.843
876 n-tridecane 122.06 184.22 0.884
878 1-methylnaphthalene 122.28 142.08 0.806
880 C6-benzene 122.40 162.30 0.843
882 C2-tetralin 122.80 160.20 0.843
884 C6-benzene 123.20 162.30 0.843

19
 D 6729

TABLE A1.1 Continued

Peak No. New Name Retention Time Molecular Mass, MWt Theoretical Mass, Rf, (C1)
886 C6-benzene 124.00 162.30 0.843
888 C13-paraffin 125.60 184.22 0.883
890 Trans-7-decene 126.34 140.20 0.874
892 n-tetradecane 126.60 198.34 0.883
895 2,6-dimethylnaphthalene 126.84 156.30 0.812
900 2,7-dimethylnaphthalene 126.97 156.30 0.812
905 n-tetradecane 127.10 198.34 0.883
910 1,3-dimethylnaphthalene 127.52 156.30 0.812
915 1,6-dimethylnaphthalene 127.69 156.30 0.812
920 1,5-dimethylnaphthalene 128.44 156.30 0.812
925 1,4-dimethylnaphthalene 128.31 156.30 0.812
930 Acenaphthalene 129.05 156.30 0.801
940 1,2-dimethylnaphthalene 129.92 156.30 0.812
950 n-pentadecane 131.10 212.34 0.883

20
 D 6729
TABLE A1.2 Repeatability and Reproducibility of IHA Determinations

NOTE 1—Brief explanation of header information:

rmin—lower 95 % confidence limit of rest,
rest—repeatability estimate in percent of concentration,
rmax—upper 95 % confidence limit of rest,
Rmin, Rest, Rmax—same as above except for reproducibility,
Cmin—lower concentration limit that rest, Rest is applicable, and
Cmax—upper concentration limit that rest, Rest is applicable.
NOTE 2—Short analyte names were used for the above table and by using the number beside this name, it will correspond to a full name in Annex
A1.
NOTE 3—C2benzene refer to grouping ethylbenzene, M, P, and O-xylene as a group.
NOTE 4—The numbers in the second column were used for the statistical analysis for the round robin for 1996. The numbers beside the names are the
new numbers being used in the new presentation of the IHA Method.

IHA/
GC/MS No. for RR IHA No. abbreviated rmin rest rmax Rmin Rest Rmax Cmin Cmax
Name
A
6 6 iC4 9.8 1.4 17.7 24.9 30.7 37.3 0.04 2.86
A
9 9 1C4= 10.4 16.7 25.1 28 36 45.4 0.01 0.14
A
11 12 nC4 10 12 14.2 27.1 31.7 36.6 0.92 8.51
A
12 14 t2C4= 12.1 15.7 19.8 28.2 36.8 47.1 0.03 0.31
A
14 18 c2C4= 14.2 15.4 16.7 25.2 31.1 37.9 0.03 0.29
A
20 24 3M1C4= 7.3 9.6 12.3 17.2 19.9 22.7 0.02 0.11
A
22 26 iC5 4.6 5.4 6.3 13.4 15.5 17.9 2.39 12.09
A
26 32 1C5= 5.9 7.5 9.4 17 20.6 24.7 0.06 0.4
A
28 36 2M1C4= 4.4 6.3 8.6 14.5 17.5 20.9 0.14 0.8
A
30 38 nC5 4.2 6.2 8.7 13.9 16.1 18.5 1 5.18
A
34 42 t2C5= 4.1 6.3 9.1 13 17.3 22.6 0.27 1.08
A
38 46 c2C5= 5.2 7.7 11 14.4 18.3 22.9 0.15 0.59
A
40 50 2M2C4= 3.9 6.2 9.2 15.2 18.1 21.4 0.44 1.78
A
42 52 t13C5=,= 4.5 10.2 19.6 22.1 31.1 42.2 0.01 0.05
A
52 62 222DMC4 2.9 3.7 4.7 9.8 12.9 16.6 0.07 2.16
A
54 64 cyC5= 4.6 9 15.5 15.6 20.3 25.9 0.07 0.25
A
56 66 4M1C5= 11.2 14.8 19 22.6 31.8 43.2 0.02 0.1
A
58 68 3M1C5= 8.3 12.1 17 37.1 50.5 66.8 0.04 0.12
A
62 72 cyC5 2.5 4.7 7.7 11.8 13.4 15.1 0.07 0.69
A
64 74 23DMC4 1.7 2.7 3.9 8.6 9.8 11.1 0.53 1.91
A
66 76 MTBE 1.9 3.2 5 9.1 12.3 16.2 0.12 15.73
A
70 80 c4M2C5= 5.1 7.1 9.7 27.4 43.7 65.4 0.02 0.09
A
74 82 2MC5 2.2 2.9 3.8 9.3 11 12.9 1.03 5.62
A
76 84 t4M2C5= 4.9 6.3 7.9 16.9 20.2 23.9 0.05 0.26
A
80 88 3MC5 2 2.7 3.5 7.7 9.1 10.7 0.58 3.25
A
84 92 2M1C5= 3.6 5.1 7 9.6 12.5 16.1 0.09 0.45
A
86 94 1C6= 3.9 6.4 9.9 15.1 19.9 25.7 0.04 0.26
A
96 104 nC6 2.5 4.6 7.7 11 13.3 15.8 0.25 3.23
A
98 106 c3C6= 4.4 6.5 9.1 12.5 16.3 20.9 0.08 0.48
A
102 110 t3C6=+C6=,= 2.9 5.2 8.4 9.4 12.4 15.9 0.17 0.93
A
103 112 2M2C5= 2.7 4.7 7.4 9.9 12 14.4 0.15 0.77
A
104 114 3McyC5= 7.8 11.3 15.9 22.7 25.2 28 0.02 0.11
A
105 116 t3M2C5= 4.3 6.9 10.2 10.1 12.5 15.4 0.1 0.48
A
106 118 c2C6= 4.1 6.7 10.2 14.3 17.4 21 0.07 0.4
A
109 122 c3M2C5= 3.1 4.5 6.4 9.1 10.5 12.1 0.14 0.75
A
112 128 McyC5 2.4 3.3 4.4 9.1 10.1 11.1 0.36 2.34
A
116 138 24DMC5 1.8 2.7 3.9 8 10.1 12.4 0.2 1.93
A
118 142 223TMC4 0.5 4.1 14.3 20.9 35.2 54.8 0.01 0.06
A
124 150 C7=,= 0 3.1 16.6 11.3 19.1 29.9 0.01 0.04
A
128 154 methyl- 5.5 9.1 14.1 14.9 20.3 26.8 0.01 0.03
enecyC5
A
130 156 Benzene 2.6 4.7 7.8 11.5 13.8 16.5 0.15 1.86
A
131 158 1McyC5= 4.3 6.3 8.9 18.5 24.1 30.7 0.17 0.92
A
133 162 c2M3C6= 0 1.2 6.8 17 29.1 45.9 0.01 0.06
A
134 164 33DMC5+5M1C6= 2.3 3.9 6.2 8.5 14.8 23.6 0.02 0.22
A
136 166 cyC6 3.3 4.4 5.7 11.3 12.8 14.5 0.04 0.87
A
138 168 t2M3C6= 4.2 8.4 14.7 84.2 103.2 124.8 0.02 0.32
A
146 176 t2e3m1C4= 3.2 5.7 9.1 20.8 29.6 40.8 0.02 0.19
A
148 178 4M1C6= 0.1 2.4 11.5 16.8 29.3 46.6 0.01 0.05
A
154 184 4M2C6= 3 4.5 6.4 15.9 18.7 21.8 0.03 0.29
A
156 186 2MC6+C7= 1.4 2.1 3 6.2 7.7 9.5 1.09 3.54
A
160 190 cyC6= 3.9 7.2 12.1 30.1 45.4 65.2 0.02 0.13
A
166 198 3MC6 1.3 2 2.8 8.5 9.9 11.5 0.36 2.38
A
172 204 t13DMcyC5 1.7 2.4 3.3 10.5 11.3 12.2 0.12 0.6
A
174 206 c13DMcyC5 1.9 2.7 3.6 9.8 10.7 11.6 0.09 0.49
A
176 208 t12DMcyC5 2.2 3.2 4.3 7.6 9.1 10.8 0.05 0.46
A
180 210 3EC5 2.8 4.8 7.6 10 13.4 17.6 0.02 0.21

21
 D 6729

TABLE A1.2 Continued

IHA/
GC/MS No. for RR IHA No. abbreviated rmin rest rmax Rmin Rest Rmax Cmin Cmax
Name
A
184 212 5M-1-C6= 1.8 5 10.6 24.1 35.2 49.1 0.03 0.19
A
186 214 224TMC5 2.3 3.4 4.9 7.6 13.2 21.1 0.09 23.25
A
188 218 1C7= 4.3 6.8 10.1 15.8 20.9 26.9 0.02 0.13
A
189 220 C7= 5.2 7.8 11.1 15.1 18.3 22 0.02 0.13
A
194 226 C7= 3.3 4.8 6.8 16.6 20.7 25.2 0.02 0.16
A
196 228 C7=,= 3.7 5 6.5 12.5 17.2 22.8 0.04 0.31
A
197 230 C7=,= 5.6 7.3 9.3 19.5 23 26.9 0.04 0.26
A
198 232 C7= 3.8 4.7 5.7 42.9 60.4 82.1 0.05 0.45
A
200 234 nC7 1.5 2.2 3.2 7.4 8.9 10.7 0.13 1.55
A
202 236 c3C7= 2.1 3 4.2 14.2 18.2 23 0.04 0.36
A
204 238 2M2C6= 2.1 3 4.3 14.4 16.5 18.7 0.05 0.43
A
206 240 c3M3C6= 3.3 4.5 6.1 21 24.9 29.3 0.03 0.29
A
208 242 t3C7= 1.8 2.7 4 12.9 15.2 17.8 0.04 0.35
A
210 244 3E2C5= 0.1 1.2 5.4 13.4 16.6 20.4 0.02 0.13
A
212 246 1,5DMcyC5= 3 5 7.8 10.3 16.2 24 0.03 0.27
A
214 248 t2M3C6= 2.8 3.6 4.7 13.8 17.9 22.9 0.04 0.33
A
218 252 23DM2C5= 3.1 4 5 9.1 13 17.8 0.04 0.56
A
222 256 McyC6 1.9 2.6 3.6 8.5 9.9 11.5 0.16 1.44
A
224 260 113TMCyC5 1.7 5.1 11.5 10.8 14.4 18.7 0.01 0.09
A
226 262 22DMC6 4.7 9.2 15.9 12.9 23.2 38.1 0.01 0.07
A
234 270 EcyC5 2.5 3.6 5 9.6 13.5 18.4 0.04 0.3
A
240 276 223TMC5 2.2 4.9 9.3 14.1 27.3 46.7 0.02 0.54
A
245 278 25DMC6+C8= 1.5 2.8 4.7 6.3 8.1 10.3 0.17 1.58
A
250 280 24DMC6 1.8 2.9 4.5 6.1 8.1 10.4 0.25 2.19
A
260 284 tc124TMcyC5 2.4 3.7 5.4 10.8 15.1 20.5 0.03 0.16
A
265 286 3,3DMC6+C8= 1.3 5.4 14.1 8.7 14.8 23.2 0.01 0.07
A
278 292 tc123TMcyC5 6.1 11.5 19.5 40.9 70 110.3 0.03 0.09
A
290 298 C8=’S 0.3 3.2 11.8 15.5 20.3 26.1 0.02 0.23
A
292 300 234TMC5 1.9 3.2 5 8.7 12 16 0.09 9.14
A
294 302 C7=,= 2.9 4.2 5.8 19.2 41.1 75.2 0.06 0.51
A
300 304 Toluene 1.7 3.1 5.3 8.7 16.6 28.2 2.52 13.14
A
312 316 C8= 3.9 6 8.7 26 35.7 47.6 0.02 0.2
A
314 320 23DMC6 2.2 3.5 5.2 16.1 30.6 51.9 0.18 2.06
A
316 322 2M3EC5 2.3 4.5 7.9 21.3 40 67.2 0.03 0.31
A
318 324 112TMcyC5+C7=,=,=
0.4 3.3 11.8 26.6 33.7 42 0.02 0.23
A
326 332 2MC7 3.3 4.4 5.9 8.4 11.2 14.5 0.14 0.93
A
328 334 4MC7 3.5 5.6 8.3 12.5 24.4 42.4 0.15 0.5
A
334 340 c13DMcyC6 3.7 4.8 6.2 18.7 32.6 52.1 0.04 0.25
A
336 344 3MC7 2.3 3.3 4.5 17.8 21.9 26.5 0.15 1.04
A
338 346 3EC6 4.1 6.4 9.4 34.8 53 76.7 0.04 0.21
A
352 360 c1E3McyC5 3.1 4.3 5.7 8.6 23.2 48.7 0.09 2.32
A
356 364 t1E3McyC5 3.8 5.1 6.7 24.4 35.5 49.7 0.03 0.21
A
360 366 t1E2McyC5 4.5 7.7 12.3 32.3 54.1 84.1 0.02 0.11
A
362 368 1M1EcyC5 0.2 3.1 12.5 24.1 33.3 44.7 0.01 0.08
A
366 372 C8= 7.2 9.9 13.3 27.1 37 49 0.01 0.08
A
368 374 t12DMcyC6 2.2 4.8 9 63.9 97.3 140.6 0.02 0.15
A
372 378 C8=’S 3.4 5.3 7.9 109.3 124.4 141 0.02 0.26
A
374 380 t-3-C8= 0 1.5 9.4 50.8 67.2 86.9 0.02 0.12
A
380 382 C8= 3.6 5.4 7.9 21.1 38.9 64.7 0.03 0.33
A
385 384 t13DMcyC6 3.1 5.4 8.4 34.1 48.5 66.5 0.04 0.31
A
400 388 nC8 3 3.7 4.5 8.8 11.9 15.6 0.1 0.89
A
406 394 t2C8= 3 6.5 12.2 45.6 72.5 108.4 0.02 0.28
A
408 396 iPrcyC5 5.8 7.4 9.3 31.7 50.8 76.5 0.03 0.36
A
416 404 C9= 0.3 2.9 9.9 46.9 63.8 84.4 0.02 0.14
A
422 410 C9=’S 4.8 8 12.4 30.5 43.2 58.9 0.02 0.17
A
432 420 c12DMcyC6 3.4 4.9 6.8 22.1 39.3 63.8 0.04 0.39
A
434 422 24DMC7 5.6 9.9 15.9 54.5 105.5 181.2 0.02 0.09
A
436 424 C9= 1.9 6 13.7 34.7 47.5 63.1 0.01 0.07
A
438 426 C9= 4.1 6.6 10 19 27.7 38.7 0.02 0.11
A
440 428 EcyC6 2.7 5 8.2 14.1 22 32.5 0.03 0.28
A
444 432 2M4EC6 7.7 11.1 15.3 20.2 27.4 36 0.01 0.03
A
446 434 26DMC7 5.9 7.3 8.9 21.9 27.7 34.4 0.03 0.14
A
450 438 114TMcyC6 5.9 8.2 11 28 42.1 60.3 0.03 0.21
A
458 446 25&35DMc7 3.7 5.9 8.7 10.5 14.9 20.5 0.07 0.25
A
460 448 C9=’S 3.3 8.4 17.1 40.1 56.4 76.6 0.01 0.07
A
462 450 33DMC7 0.1 3.3 15.7 25 44 70.9 0.01 0.05
A
475 460 EBenzene 2.8 3.9 5.4 7.2 8.9 10.9 0.66 3.12
A
480 464 t124TMcyC6 6.9 10.9 16.3 84.7 109.3 138.2 0.02 0.15
A
500 474 M-Xylene 2.7 3.7 5 7.5 9.2 11 1.67 7.93
A
502 476 P-Xylene 3.1 4.4 5.9 8.8 11.6 14.8 0.63 3.26
A
503 478 23DMC7 5.1 7.6 10.9 45.3 73.5 111.5 0.03 0.16
A
504 480 35DMC7 7.2 9.8 13 44.1 82.8 139.2 0.02 0.07

22
 D 6729

TABLE A1.2 Continued

IHA/
GC/MS No. for RR IHA No. abbreviated rmin rest rmax Rmin Rest Rmax Cmin Cmax
Name
A
506 482 34DMC7 6.5 10.1 15 42.5 67.7 101.4 0.02 0.07
A
510 486 3M3EC6 6.3 10 15 38 61 92 0.02 0.14
A
518 492 4MC8+C9= 4.1 5.9 8.1 12.4 14.3 16.3 0.05 0.3
A
520 494 2MC8 4.4 5.9 7.7 12.4 15.9 20.1 0.07 0.38
A
522 496 C9= 6.8 10.6 15.7 22.3 33.3 47.4 0.01 0.1
A
528 502 3EC7 4.5 6.8 9.8 24.7 34.4 46.3 0.02 0.11
A
530 504 3MC8 5 8 12 12.4 17.9 24.9 0.08 0.45
A
550 512 O-Xylene 2.1 3 4.1 7.7 9.8 12.3 0.92 4.18
A
564 518 C9P 3.1 6.6 12 31.1 50.4 76.3 0.01 0.37
A
568 522 t1E4McyC6 6.5 9.7 13.8 26.3 46.1 74.1 0.02 0.13
A
570 524 c1E4McyC6 4.7 7.4 10.8 22.1 35.8 54.2 0.02 0.15
A
572 526 C9P 4.5 7.2 10.7 28.7 55.7 95.9 0.03 0.6
A
582 532 C9P 7.5 11.1 15.6 16.9 23.1 30.8 0.02 0.24
A
586 534 t3C9= 4.6 9.1 16 27.3 38.8 53.2 0.01 0.16
A
590 536 c3C9= 7.1 11.1 16.4 23.5 36.1 52.7 0.01 0.17
A
600 540 nC9 5.8 7.2 8.7 18.3 30 45.8 0.1 0.51
A
606 546 1M1EcyC6 0.4 3.1 10.7 46.2 75.8 116 0.02 0.11
A
608 548 1M2PrcyC5 0.2 3 12.2 19.2 30.1 44.5 0.01 0.1
A
616 556 iPrbenz 4.3 6.9 10.4 11.2 18.9 29.6 0.04 0.41
A
626 566 iPrcyC6 4.4 7.7 12.4 21.8 40.2 66.9 0.01 0.35
A
636 576 sBucyC5 0.5 4.5 16.1 22.9 36.7 55.1 0.01 0.06
A
638 578 PrcyC6 4 7.3 12 77.9 96.8 118.6 0.02 0.12
A
644 584 26DMC8 4.6 8.6 14.4 41.2 68.2 105 0.03 0.23
A
646 586 36DMC8 4.5 7.7 12.3 31.6 40.4 50.8 0.03 0.11
A
651 592 nPrbenz 3.5 5.8 9 11.6 17.3 24.6 0.21 0.83
A
655 600 1E3Mbenz 2.8 4.5 6.9 6.5 8.3 10.3 0.85 2.8
A
656 602 1E4Mbenz 3.1 4.5 6.3 7.8 9.7 11.9 0.36 1.26
A
658 606 135TMbenz 3.4 5.8 9.1 8.5 12.5 17.7 0.46 1.53
A
660 610 5MC9 10.9 12.9 15.1 76.7 104.7 138.8 0.02 0.13
A
661 612 4MC9 7.1 10.2 14 29.7 44.5 63.5 0.02 0.13
A
662 614 2MC9 4.4 7.1 10.9 14.9 24.2 36.6 0.1 2.07
A
663 616 1E2Mbenz 3.6 5.5 8.1 10.3 15.9 23.2 0.3 1.1
A
668 622 3MC9 7.2 12.9 21 41.8 59 80.3 0.04 0.19
A
671 626 C10-P 0.5 5.4 19.5 30.3 52.1 82.6 0.01 0.47
A
673 630 124TMbenz 2.8 4.7 7.4 9.3 12.5 16.4 1.29 4.65
A
674 632 C10-P 7.1 12.9 21.4 35.6 81.2 155.1 0.01 0.32
A
675 634 C10P 2.6 6.2 12.3 25.2 55.1 102.4 0.01 0.34
A
684 648 C10A 5.2 9.3 15.1 22.8 38.2 59.4 0.01 0.3
A
688 652 naphthene 4.8 7.5 11 40.2 63.2 93.7 0.03 0.27
A
700 662 nC10 7.3 8.9 10.7 14.3 29.5 52.8 0.07 0.29
A
705 668 123TMbenz 4 6.3 9.2 18.2 23.2 29.1 0.28 1.15
A
708 674 1M4iPrbenz 3 6.6 12.1 22 34.2 50.1 0.01 0.08
A
709 676 C11P 5.1 8.9 14.1 34.9 68.2 118.1 0.02 0.12
A
712 680 indan 4 6.6 10.1 15.7 23.6 33.8 0.15 0.4
A
714 682 sBucyC6 8.7 12.7 17.6 46.7 70.2 100.5 0.01 0.06
A
718 686 1M2iPrbenz 4.6 8.4 13.7 48 88.1 146 0.02 0.33
A
723 694 C11P 5 7.8 11.4 29.6 60.7 108.3 0.02 0.19
A
724 696 13DEbenz 4.6 6.1 8 11.1 19.5 31.5 0.07 0.22
A
725 698 1M3Prbenz 3.5 5.2 7.3 8.5 13 18.8 0.18 0.71
A
727 702 1M4Prbenz 4.8 7.8 11.7 16.7 22.8 30.2 0.1 0.35
A
728 704 Bubenz 7.2 11 16.1 15.8 21.8 29.3 0.04 0.14
A
729 706 35DM1EBenz 3.5 6.4 10.5 9.1 14 20.3 0.18 0.56
A
730 708 12DEbenz 6.4 9.7 14 38.6 57.4 81.4 0.02 0.09
A
740 718 1M2PrBenz 6.8 10.7 15.8 27.3 41.7 60.4 0.06 0.21
A
746 722 5MC10 7.1 11.5 17.5 30.8 44.5 61.8 0.02 0.08
A
748 724 4MC10 4.2 6.9 10.4 15.3 32.1 57.9 0.01 0.68
A
750 726 2MC10 6.5 9.5 13.3 52.7 68.9 88.2 0.02 0.15
A
756 730 14DM2Ebenz 4.1 6.1 8.7 17.4 26.3 37.9 0.12 0.42
A
758 732 13DM4Ebenz 4.5 6.2 8.3 18.5 22.9 27.8 0.12 0.54
A
762 736 3MC10 10.9 15.7 21.7 35.8 54.5 78.8 0.02 0.17
A
764 740 12DM4Ebenz+ 3.1 5.3 8.5 8.2 12.5 18.2 0.27 0.75
C1indane
A
768 744 13DM2Ebenz 6.2 9.6 14 37.9 68.9 113.3 0.03 0.35
A
780 750 1M4tBubenz 6.1 10.3 16.1 45.8 83.5 137.7 0.03 0.11
A
785 752 12DM3Ebenz 4.1 7.3 11.7 28.2 45.3 68.2 0.09 0.2
A
800 756 nC11 8.7 11.1 13.9 31.2 40.2 50.6 0.04 0.21
A
806 762 1245tertM- 5.4 6.8 8.6 12.3 16.8 22.2 0.12 0.39
benz
A
810 766 1235tertM- 4.7 7.7 11.6 12.7 19.9 29.3 0.16 0.56
benz
A
824 782 C11A 8.7 11.3 14.2 32.9 55.6 86.9 0.02 0.07
A
826 784 1E2Prbenz? 5 7.5 10.7 14.2 25.2 40.8 0.09 0.44

23
 D 6729

TABLE A1.2 Continued

IHA/
GC/MS No. for RR IHA No. abbreviated rmin rest rmax Rmin Rest Rmax Cmin Cmax
Name
A
828 786 C11A 8.5 11.8 15.7 23.4 35.1 50.3 0.02 0.1
A
830 788 C11A 8.8 12.3 16.7 35.7 49.9 67.5 0.02 0.1
A
832 790 C11A 9.7 13.4 17.8 22.9 39.6 63 0.02 0.1
A
834 792 1M3Bubenz 5.6 7.9 10.9 11.1 14.8 19.2 0.08 0.35
A
836 796 1234tetraM- 6.8 9.3 12.5 24.4 36.5 52.1 0.1 0.28
benz
+C11A
A
840 800 t1M2(4MC5)cyC5 10.2 15.5 22.3 41 56.7 75.8 0.02 0.11
A
844 804 C11A 9.1 13.5 19 34 54.7 82.5 0.02 0.07
A
846 806 C11A 9.6 13.6 18.5 65.6 96.4 135.5 0.02 0.08
A
854 812 1tBu35DMbenz 11.2 15.5 20.7 36.6 62.3 97.7 0.02 0.1
A
858 814 naphthalene 4.9 6.7 8.9 15.3 25.8 40.3 0.12 0.52
A
862 817 C11A 9.7 14.4 20.5 46.5 66.5 91.4 0.02 0.16
A
870 820 16DMIND- 9 12.3 16.3 25.7 42.6 65.8 0.02 0.17
ANE
A
875 822 C11A 15.6 19.4 23.8 43.8 68.4 100.9 0.02 0.09
A
884 824 2ETHYL IN- 5.8 9.8 15.4 18.4 29 42.9 0.03 0.19
DANE
A
888 826 2ETHYL135TMBZ 7.9 12.8 19.5 39.4 59.9 86.6 0.01 0.07
A
895 832 nC12 13.4 16.7 20.6 53.4 73.9 99.1 0.02 0.15
A
915 842 24DMIND- 10.3 16.3 24.2 27.2 40 56.2 0.02 0.05
ANE
A
925 846 1tBu4Ebenz 7.7 13.1 20.7 60.2 101.8 159.2 0.04 0.16
A
930 848 13DM IN- 5.3 10.3 17.9 31.3 43 57.3 0.01 0.18
DANE
A
940 858 HEXYLbenz 9.8 15.1 21.9 61.2 96 141.8 0.01 0.13
A
942 870 2Mnaphtha- 6.4 8.9 12.1 17 21.6 27 0.04 0.64
lene
A
947 879 1Mnaphtha- 7.5 11.6 16.9 25 29.8 35.2 0.02 0.27
lene
A
The components that have been checked by GCMS by one of the participants on one of the samples that was used in the 1996 ASTM round robin.

TABLE A1.3 Group Summaries for the Gasolines Run in the 1996 ASTM Interlaboratory Cooperative Study
Name rmin rest rmax Rmin Rest Rmax Cmin Cmax
Paraffin 0.0562 0.0646 0.08 0.125 0.186 0.373 1 20
Isoparaffin 0.0209 0.024 0.03 0.047 0.065 0.102 20 65
C2Benzene 0.0334 0.0384 0.05 0.057 0.073 0.102 3 20
Oxygenates 0.0418 0.0491 0.06 0.104 0.141 0.221 3 20

A2. OXYGENATE LINEARITY STUDY

A2.1 This information is presented in Tables A2.1-A2.7 and and toluene among the indicated methods are well within the
Figs. A2.1-A2.13. reproducibilities of the methods. The sample numbers refer to
the interlaboratoy cooperative study samples. It should be
A2.2 Tables A2.2-A2.7 show comparisons between this test noted that the interlaboratory cooperative study samples in-
method and other methods for several compound types. Mul-
cluded only spark ignition fuels and different results may be
tidimensional PIONA is included since it tends to give reason-
obtained with pure blending components.
able peak compound type groupings for total olefins, total
paraffins, and total naphthenes. The differences for benzene

TABLE A2.1 Oxygenates Relative Response Factors

NOTE—All RRF relative to N-C7= 1.000; this also applies to the cooperative study.
Laboratory Laboratory Laboratory Laboratory Laboratory Laboratory Laboratory Average Standard % Standard
No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 RRF Deviation Deviation
Methanol 2.921 2.957 2.903 2.795 3.085 3.391 2.923 2.996 .194 6.465
Ethanol 1.997 2.043 2.003 2.057 2.138 2.354 2.014 2.087 .127 6.1
t-butanol 1.274 1.282 1.329 1.305 1.297 1.429 1.2 1.302 .069 5.281
MTBE 1.508 1.523 1.552 1.791 1.508 1.658 1.498 1.577 .109 6.932
ETBE 1.352 1.349 1.406 1.543 1.369 1.509 1.319 1.407 .086 6.108
TAME 1.308 1.323 1.342 1.451 1.336 1.471 1.264 1.356 .076 5.593

24
 D 6729
TABLE A2.2 Benzene
Benzene (weight %)
Sample
D 5580 D 6729
2 1.52 1.61
6 1.05 1.12
8 1.10 1.16
10 1.13 1.18
13 0.14 0.16
14 0.62 0.70
Average 0.93 0.99

TABLE A2.3 Toluene

Toluene (weight %)
Sample
D 5580 D 6729
2 4.3 4.6
6 2.1 1.9
8 10.1 11.4
10 5.0 6.1
13 3.3 2.9
14 4.4 5.3
Average 4.9 5.4

TABLE A2.4 Total Aromatics

Total Aromatics (weight %)
Sample
D 5580 PIONAA D 6729
2 30.3 28.2 32.6
6 18.9 18.7 20.0
8 49.1 49.0 51.0
10 23.9 24.5 25.4
13 19.7 19.8 22.4
14 23.8 24.6 27.5
Average 27.6 27.5 29.8
A
Multidimensional PIONA.

TABLE A2.5 Total Olefins

Total Olefins (weight %)
Sample
A
PIONA D 6729
2 7.1 4.4
6 9.8 9.4
8 6.6 6.2
10 15.1 13.7
13 11.1 11.1
14 24.6 22.2
Average 12.4 11.2
A
Multidimensional PIONA.

25
 D 6729
TABLE A2.6 Total Oxygenates
Total Oxygenates (weight %)
Sample
PIONAA Procedure B
2B 15.3 16.1
6B 7.0 8.1
8B 4.2 4.5
10C >8 10.0
13B 20.5 19.9
14B 2.8 3.2
Average N/A 10.3
A
Multidimensional PIONA.
B
Major oxygenate = MTBE.
C
Major oxygenate = Ethanol.

TABLE A2.7 Total Paraffins and Total Napthenes

Total Paraffins (weight %) Total Naphthenes (weight %)
Sample
A
PIONA D 6729 PIONAA D 6729
8 35.6 35.0 2.2 2.8
10 41.1 42.3 5.6 6.7
13 42.6 43.0 1.3 3.5
14 34.1 37.9 5.9 7.6
Average 38.4 39.6 3.8 5.2
A
Multidimensional PIONA.

26
 D 6729

FIG. A2.1 IHA Method Oxygenates Linearity Cooperative Study–Laboratory 1

27
 D 6729

FIG. A2.2 IHA Method Oxygenates Linearity Cooperative Study–Laboratory 2

28
 D 6729

FIG. A2.3 IHA Method Oxygenates Linearity Cooperative Study–Laboratory 3

29
 D 6729

FIG. A2.4 IHA Method Oxygenate Linearity Cooperative Study–Laboratory 4

30
 D 6729

FIG. A2.5 IHA Method Oxygenate Linearity Cooperative Study–Laboratory 5

31
 D 6729

FIG. A2.6 IHA Method Oxygenate Linearity Cooperative Study–Laboratory 6

32
 D 6729

FIG. A2.7 IHA Method Oxygenate Linearity Cooperative Study–Laboratory 7

33
 D 6729

FIG. A2.8 Determination of Calculated Oxygenate Response from IHA Method–Methanol

FIG. A2.9 Determination of Calculated Oxygenate Response from IHA Method–Ethanol

FIG. A2.10 Determination of Calculated Oxygenate Response from IHA Method–t-Butanol

34
 D 6729

FIG. A2.11 Determination of Calculated Oxygenate Response from IHA Method–MTBE

FIG. A2.12 Determination of Calculated Oxygenate Response from IHA Method–ETBE

35
 D 6729

FIG. A2.13 Determination of Calculated Oxygenate Response from IHA Method–TAME

APPENDIX

(Nonmandatory Information)

X1. BIBLIOGRAPHY

X1.1 The following publications on DHA analyses may be X1.1.5 Di Sanzo, F. P. and Giarrocco, V. G., “Analysis of
useful as background and are recommended to the user of these Pressurized Gasoline-Range Liquid Hydrocarbon Samples by
test procedures: Capillary Column and PIONA Analyzer Gas Chromatogra-
X1.1.1 Johansen, N.G. and Ettre, L.S., “Retention Index phy,” Journal of Chromatographic Science, Vol 26, June 1988,
Values of Hydrocarbons on Open Tubular Columns Coated pp 258-266
with Methyl Silicone Liquid Phases,” Chromatographia, Vol 5, X1.1.6 Durand, J. P., Beboluene, J. J. and Ducrozet, A.,
No. 10, Oct 1982 “Detailed Characterization of Petroleum Products with Capil-
X1.1.2 Johansen, N.G., Ettre, L.S., and Miller, R.L., “Quan- lary GC Analyzers,” Analusis, 23, 1995, pp 481-483
titative Analysis of Hydrocarbons by Structural Group Type in X1.1.7 Canadian General Standards Board: CAN/CGSB
Gasolines and Distillates. Part 1,” Journal of Chromatography,
-3.0, No.14.3-94, “Test Method for Individual Hydrocarbon
256, 1983, pp. 393-417
Component Analysis (IHA) in Spark Ignition Engine Fuels by
X1.1.3 Kopp, V.R., Bones, C.J., Doerr, D.G., Ho, S.P., and
Gas Chromatography”
Schubert, A.J., “Heavy Hydrocarbon/Volatility Study: Fuel
Blending and Analysis for the Auto/Oil Air Quality Improve- X1.1.8 French Standard NF N07-086, December 1995,
ment Research Program,” SAE Paper No. 930143, March 1993 “Determination of Hydrocarbon Type Contents in Motor Gaso-
X1.1.4 Schubert, A.J. and Johansen, N.J., “Cooperative lines from Detailed Analysis Capillary Gas Chromatography”
Study to Evaluate a Standard Test Method for the Speciation of
Gasolines by Capillary Gas Chromatography,” SAE Paper No.
930144, March 1993

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36