D 6730 - 01 Astm
D 6730 - 01 Astm
D 6730 - 01 Astm
Designation: D 6730 – 01
1
This test method is under the jurisdiction of ASTM Committee D02 on
2
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee Annual Book of Standards, Vol 05.01.
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D02.04.0Lon Gas Chromatographic Methods. Discontinued; see 1999 Annual Book of ASTM Standards, Vol 05.01.
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Current edition approved Nov. 10, 2001. Published January 2002. Annual Book of Standards, Vol 05.02.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
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D 6730 – 01
Petroleum Products4 control and product specification compliance for many indi-
D 4177 Practice for Automatic Sampling of Petroleum and vidual hydrocarbons can be determined through the use of this
Petroleum Products4 test method.
D 4307 Practice for Preparation of Liquid Blends for Use as 5.2 This test method is adopted from earlier development
Analytical Standards4 and enhancement.7,8,9,10 The chromatographic operating con-
D 4626 Practice for Calculation of Gas Chromatographic ditions and column tuning process, included in this test
Response Factors4 method, were developed to provide and enhance the separation
D 4815 Test Method for Determination of MTBE, ETBE, and subsequent determination of many individual components
TAME, DIPE, tertiary-Amyl Alcohol and C1 to C4 Alco- not obtained with previous single-column analyses. The col-
hols in Gasoline by Gas Chromatography4 umn temperature program profile is selected to afford the
D 5580 Test Method for Determination of Benzene, Tolu- maximum resolution of possible co-eluting components, espe-
ene, Ethylbenzene, p/m-Xylene, o-Xylene, C9 and Heavier cially where these are of two different compound types (for
Aromatics and Total Aromatics in Finished Gasoline by example, a paraffin and a naphthene).
Gas Chromatography5 5.3 Although a majority of the individual hydrocarbons
D 5599 Test Method for Determination of Oxygenates in present in petroleum distillates are determined, some co-
Gasoline by Gas Chromatography and Oxygen Selective elution of compounds is encountered. If this test method is
Flame Ionization Detection5 utilized to determine bulk hydrocarbon group-type composi-
D 5623 Test Method for Sulfur Compounds in Light Petro- tion (PONA), the user of such data should be cautioned that
leum Liquids by Gas Chromatography and Sulfur Selec- some error will be encountered due to co-elution and a lack of
tive Detection5 identification of all components present. Samples containing
E 355 Practice for Gas Chromatography Terms and Rela- significant amounts of olefinic or naphthenic, or both, constitu-
tionships6 ents above octane may reflect significant errors in PONA-type
E 594 Practice for Testing Flame Ionization Detectors Used groupings.
in Gas or Supercritical Fluid Chromatography6 5.4 If water is or is suspected of being present, its concen-
E 1510 Practice for Installing Fused Silica Open Tubular tration is determined by the use of Test Method D 1744. Other
Capillary Columns in Gas Chromatography6 compounds containing oxygen, sulfur, nitrogen, and so forth
may also be present, and may co-elute with the hydrocarbons.
3. Terminology When known co-elution exists, these are noted in the test
3.1 Definitions—This test method makes reference to many method data tables. If determination of these specific com-
common gas chromatographic procedures, terms, and relation- pounds is required, it is recommended that test methods for
ships. Detailed definitions can be found in Practice E 355. these specific materials be used, such as Test Method D 4815
and D 5599 for oxygenates, Test Method D 5580 for aromatics,
4. Summary of Test Method and Test Method D 5623 for sulfur compounds.
4.1 A representative sample of the petroleum liquid is 6. Apparatus
introduced into a gas chromatograph equipped with an open
tubular (capillary) column coated with a methyl silicone liquid 6.1 Gas Chromatograph—Instrumentation capable of col-
phase, modified with a capillary precolumn. Helium carrier gas umn oven temperature programming, from subambient (5°C)
transports the vaporized sample through the column, in which to at least 200°C, in 0.1°C/min or less rate increments, is
it is partitioned into individual components which are sensed required. Multi-step column oven temperature programming is
with a flame ionization detector as they elute from the end of required, consisting of an initial hold time, an initial tempera-
the column. The detector signal is presented on a strip chart ture program followed by an isothermal temperature hold and
recorder or digitally, or both, by way of an integrator or another programmed temperature rise. A heated flash vaporiz-
integrating computer. Each eluting component is identified by ing injector designed to provide a linear sample split injection
comparing its retention time to that established by analyzing (that is, 200:1) is required for proper sample introduction. The
reference standards or samples under identical conditions. The associated carrier gas controls must be of sufficient precision to
concentration of each component in mass % is determined by provide reproducible column flows and split ratios in order to
normalization of the peak areas after correction with detector maintain analytical integrity. A hydrogen flame ionization
response factors. Unknown components are reported as a total
unknown mass %.
7
Johansen, N.G., and Ettre, L.S., “Retention Index Values of Hydrocarbons on
Open Tubular Columns Coated with Methyl Silicone Liquid Phases,” Chro-
5. Significance and Use
matographia, Vol 5, No. 10, October 1982.
5.1 Knowledge of the individual component composition 8
Johansen, N.G., Ettre, L.S., and Miller, R.L., “Quantitative Analysis of
(speciation) of gasoline fuels and blending stocks is useful for Hydrocarbons by Structural Group Type in Gasolines and Distillates. Part 1,”
Journal of Chromatography, 256, 1983, pp. 393-417.
refinery quality control and product specification. Process 9
Kopp, V.R., Bones, C.J., Doerr, D.G., Ho, S.P., and Schubert, A.J., “Heavy
Hydrocarbon/Volatility Study: Fuel Blending and Analysis for the Auto/Oil Air
Quality Improvement Research Program,” SAE Paper No. 930143, March 1993.
10
Schubert, A.J. and Johansen, N.J., “Cooperative Study to Evaluate a Standard
5
Annual Book of Standards, Vol 05.03. Test Method for the Speciation of Gasolines by Capillary Gas Chromatography,”
6
Annual Book of Standards, Vol 14.02. SAE Paper No. 930144, March 1993.
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D 6730 – 01
detector, with associated gas controls and electronics, designed 7. Reagents and Materials
for optimum response with open tubular columns, shall con- 7.1 Carrier Gas—Helium, 99.999 % pure. (Warning—
form to the specifications as described in Practice E 594, as Helium, air, nitrogen, compressed gas under pressure.)
well as having an operating temperature range of up to at least 7.2 Oxidant—Air, 99.999 % pure. (Warning—see 7.1.)
250°C. 7.3 Detector Makeup Gas—Nitrogen, 99.999 % pure.
6.2 Sample Introduction—Manual or automatic liquid (Warning—see 7.1.)
sample injection to the splitting injector may be employed. 7.4 Fuel Gas—Hydrogen, 99.999 % pure. (Warning—
Automated injections are highly recommended. Micro- Hydrogen, flammable gas under high pressure.)
syringes, auto-syringe samplers, or valves capable of 0.1 to 0.5 7.5 Reference Standards:
µL. injections are suitable. It should be noted that some 7.5.1 Purity of Reagents—Reagent grade chemicals shall be
syringes and improper injection techniques as well as inad- used in all tests. Unless otherwise indicated, it is intended that
equate splitter design could result in sample fractionation. This all reagents conform to the specifications of the Committee on
must be determined in accordance with Section 10. Analytical Reagents of the American Chemical Society11
6.3 Electronic Integrator—Any electronic integration de- where such specifications are available. Other grades may be
vice used for quantitating these analyses shall meet or exceed used, provided it is first ascertained that the reagent is of
these minimum requirements: sufficiently high purity to permit its use without lessening the
6.3.1 Capacity to handle 400 or more peaks per analysis. accuracy of the determination.
7.5.2 Methanol—(Warning—These materials are flam-
6.3.2 Normalized area percent calculation with response mable and may be harmful or fatal, if ingested or inhaled.).
factors. 7.5.3 Ethanol—Only absolute ethanol of 99.5 minimum
6.3.3 Noise and spike rejection. percent meets the requirements of this test method.
6.3.4 Accurate area determination of fast (1 to 2 s) peaks (10 (Warning—see 7.5.2.)
Hz or greater sampling rate). 7.5.4 Hydrocarbon and Other Component References—
6.3.5 Maintain peak detection sensitivity for narrow and Individual and mixed component reference materials are com-
broad peaks. mercially available and may be used to establish qualitative
6.3.6 Positive and negative sloping baseline correction. and quantitative calibration. (Warning—see 7.5.2.)
7.5.5 System and Column Evaluation Mixture—A quantita-
6.3.7 Perpendicular drop and tangent skimming as needed.
tively prepared mixture, complying with Practice D 4307, of
6.3.8 Display of baseline used to ensure correct peak area individual hydrocarbons and oxygenates of interest is used for
determination. system and column evaluation (see Table 1). (Warning—see
6.4 Open Tubular Column—The column used for this test 7.5.2.) Fig. 1 is a chromatogram of the recommended mixture
method consists of a primary (100 m) analytical column and a in Table 1.
precolumn. The ability to provide the required component
separations is dependent on the precise control of the column 8. Sampling
selectivity, which is typically slightly more than that exhibited 8.1 Hydrocarbon liquids with Reid vapor pressures of 110
by current commercially available columns. Some older col- kPa (16 psi) or less may be sampled either into a floating piston
umns, and columns that have a sample residue from repeated cylinder or into an open container (Practices D 4057 and
use without conditioning, may exhibit the required polarity. D 4177). If the sample as received does not meet the upper
Until adequate columns are commercially available, the cur- boiling range requirements of 1.1, it may be necessary to
rently used methyl silicone columns can be modified or tuned extend the analysis time and raise the upper column tempera-
to meet the method column specifications. See Section 11 for ture of this test method to ensure complete elution of higher
a description of the column performance specifications and boiling range sample material from the column.
Annex A1 for a description of the column modification 8.1.1 Piston Cylinder Sampling—Refer to Practice D 3700
procedure. for instructions on transferring a representative sample of a
6.4.1 The primary gas chromatographic column used for hydrocarbon fluid from a source into a floating piston cylinder.
this test method will meet the following specifications. Add inert gas to the ballast side of the floating piston cylinder
Material fused silica to achieve a pressure of 350 kPa (45 psi) above the vapor
Length 100 m pressure of the sample.
Internal diameter 0.25 mm
Liquid phase methyl silicone
8.1.2 Open Container Sampling—Refer to Practice D 4057
Film thickness 0.50 µm for instructions on manual sampling from bulk storage into
Theoretical plates, n, pentane at 35°C ; 400 000 to 500 000 open containers. Stopper the container immediately after tak-
Retention factor, k, pentane at 35°C 0.45 to 0.50
Resolution, R, t-butanol and 2-methylbutene-2 at 3.25 to 5.25
ing a sample.
35°C
Peak symmetry, t-butanol at 35°C > 1.0 to < 5.0
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6.4.2 Precolumn—A variable length (1 to 4 m) of 5 % Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
phenyl/95 % dimethylpolysiloxane fused silica open tubular
listed by the American Chemical Society, see Analar Standards for Laboratory
column (0.25 mm inside diameter) is added to the front Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and
(injector) end of the 100 m column, as described in Annex A1. National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
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D 6730 – 01
TABLE 1 System and Column Evaluation Mixture average linear gas velocity: uave ~cm/s! 5 column length ~cm!/tM~s!
% (1)
Ethanol 8.00 9.5 After final adjustment of the carrier gas flow rate, note
n-pentane 2.00
t-butanol 0.50
the carrier gas inlet pressure. Measure and, if necessary,
2-methylbutene-2 2.50 readjust the injector split flow rate to give the specified or
2,3-dimethylbutane 0.50 desired split ratio. Calculate the column outlet flow rate using
Methyl-t-butyl ether 10.00
n-hexane 2.00
9.5.1 and the split ratio using 9.5.2.
1-methylcyclopentene 0.50 9.5.1 Column Carrier Gas Flow Rate (at outlet):
Benzene 1.00
Cyclohexane 28.90
9.5.1.1 P = (head pressure (psig) + ambient pressure)/
3-ethylpentane 0.20 ambient pressure.
1,2t-dimethylcyclopentane 0.50 9.5.1.2 j = compressibility factor = 3/2((P2−1)/(P3−1)).
n-heptane 2.00
2,3,3-trimethylpentane 0.50 9.5.1.3 uo= uave/j = column outlet velocity.
Toluene 7.00 9.5.1.4 Ac= pi(r)2= column cross-sectional area (cm2).
n-octane 2.00
Ethylbenzene 25.00 where r = column internal radius (cm).
p-xylene 1.00 9.5.1.5 Flow rate (cm3/min) = u03 Ac3 60.
2,3-dimethylheptane 0.20
n-nonane 2.00 9.5.2 Injection Split Ratio—(Split flow rate + column flow
5-methylnonane 0.20 rate)/column flow rate.
1-methyl-2-ethylbenzene 0.50
n-decane 1.00
9.5.3 Example—Using a 100–m 3 0.25–mm capillary col-
n-undecane 0.50 umn:
1,2,3,5-tetramethylbenzene
Naphthalene
0.25
0.50
9.5.3.1 Uave= 1003 100/6.98 3 60 = 23.88 cm/s.
n-dodecane 0.25 9.5.3.2 P = 40 psig + 12.0/12.0 = 4.33.
1-methylnaphthalene 0.25
n-tridecane 0.25
9.5.3.3 j = 3/2((18.778-1)/(81.370-1)) = 0.33
9.5.3.4 uo= 23.88/0.33 = 71.96 cm/s.
9.5.3.5 Ac= pi(0.025/2)2= 4.9 3 10−4 cm2.
9.5.3.6 Flow rate = 71.96 3 4.9 3 10−43 60 = 2.12
8.2 Preserve the sample by cooling to approximately 4°C cm3/min.
and maintaining that temperature prior to analysis.
9.5.3.7 Split Ratio = (192 + 2.12)/2.12 = 91.6:1.
8.3 Transfer an aliquot of the cooled sample to a precooled
septum vial and seal immediately. 9.6 Make a blank analysis (no sample injection) run to
8.4 Obtain the test specimen for analysis directly from the ensure proper instrument operation and further condition the
sealed septum vial, for either manual or automatic injection. column and instrumentation. If stray peaks or a rising baseline
signal is observed, the column oven shall be kept at the upper
9. Preparation of Apparatus temperature until the baseline becomes steady and returns to
within approximately 5 % of the starting temperature detector
9.1 Install the 100–m column and, if required, a precolumn
signal.
according to the manufacturer’s or supplier’s instructions and
Annex A1. See Practice E 1510 for recommended installation 9.7 After any extended conditioning period, or if the instru-
procedures. ment has been shut down, it is advisable to repeat 9.4, 9.5, and
9.2 Determine the required length of the precolumn in 9.6 to ensure proper carrier gas flows are being used and the
accordance with Annex A1. Adjust the operating conditions of column is clean.
the gas chromatograph to those listed in Table 2 or as
determined by Section 12 and Annex A1. 10. Split Injection Linearity
9.3 During setup and, when not performing analyses, it is 10.1 Splitting injector linearity must be established to de-
advisable to turn off the cryogenic operation and set the column termine proper quantitative parameters and limits. The split
oven temperature at 35°C. Attach the column outlet to the ratio used is dependent upon the split linearity characteristics
flame ionization detector inlet and check for leaks throughout of the particular injector and the sample retention factor of the
the system. If leaks are found, tighten or replace fittings before column. The retention factor of a particular column for a
proceeding. sample component is proportional to the amount of liquid
9.4 Confirm or adjust, or both, the column carrier gas flow phase (loading or film thickness) and the ratio of the column
rate by making injections of methane or natural gas. The temperature to the component boiling point (vapor pressure).
methane retention time shall be 7.00 6 0.02 min with the Overloading of the column may cause loss of resolution for
column oven temperature at 35°C, which results in an average some components and, since overloaded peaks are skewed,
linear velocity of 24 cm/s, as determined using Eq 1. This will variance in retention times. This can lead to erroneous com-
result in a methane retention time of 6.53 min at 5°C. Raising ponent identification. During column evaluations and split
or lowering the carrier gas pressure to the injector makes flow linearity studies, be aware of any peaks that may appear front
rate adjustment. A starting point of 277–kPa (40–psig) helium skewed, indicating column overload. Note the component size
pressure is recommended, although columns requiring as high and avoid conditions leading to this problem during actual
as 332–kPa (48–psig) helium have been encountered. analyses.
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TABLE 2 GC Operating Conditions 11.2 Calculate the retention factor (k) for pentane at 35°C:
Column Temperature Program k 5 ~tR 2 tM!/tM (3)
Initial temperature 5°C
Initial time 10 min. where:
First program rate 5.0°/min tM = gas holdup time (methane), and
First hold temperature 50°C
First hold time to the elution of ethylbenzene (;50 min) tR = retention time for pentane, min.
Second program rate 1.5°/min 11.2.1 The retention factor must be between 0.45 and 0.50
Final temperature 200°C
Final hold time 5 min
for proper application of this test method.
Injector 11.3 Calculate the column efficiency using the pentane
Temperature 250°C
peak:
Split ratio 150:1 n 5 5.545 ~tR/w1/2h!2 (4)
Sample size 0.1 - 0.2 µL
Detector where:
Type flame Ionization n = column efficiency (theoretical plates),
Temperature 250°C tR = retention time of pentane, and
Use manufacturers recommended detector gas flows or: w1/2h = peak width at half height.
Fuel gas hydrogen at 30 mL/min
Oxidant air at 300 mL/min 11.3.1 The column efficiency must be at least 400 000 plates
Make-up gas, where required nitrogen at 20 mL/min for proper application of this test method.
Carrier Gas 11.4 The selectivity of apparently identical columns toward
Type helium hydrocarbons may vary regarding oxygenated compounds;
Pressure ; 277 kPa (40 psig)
Average linear velocity 24 cm/s at 35°C
either due to extraneous materials in the liquid phase, or due to
activity of the column wall surface. The addition of a precol-
umn has little if any affect on the selectivity toward oxygenates
10.2 Set the injector temperature and split ratio to the (see Annex A1, Fig. A1.4). The relative resolution of oxygen-
following values and, for each set of conditions inject the listed ates is inherent to the quality of the primary 100–m column,
quantities of the system and column evaluation mixture (7.5.5), and is specified by the resolution of t-butanol from
using the operating conditions listed in Table 2 or as deter- 2-methylbutene-2 at 35°C. Calculate the resolution:
mined in Section 12. R 5 2~tR22M2Butene22 2 tRTBA!/1.699~w1/2h22M2Butene22 1 w1/2hTBA!
injector temperature: 250°C<
split: 100:1
> sample: 0.2 µL, 0.5 µL, 1.0 µL
(5)
split: 200:1
split: 100:1 11.4.1 The resolution for this pair at 35°C must be between
injector temperature: 300°C< > sample: 0.2 µL, 0.5 µL, 1.0 µL
split: 200:1 3.25 and 5.25.
10.3 Compare the calculated concentrations to the known 11.5 Extraneous column effects, or instrumental effects such
standard concentrations after calculating the corrected area as an active injector liner, may cause adsorption of oxygenated
normalization using the response factors from 13.2 and Table compounds, commonly seen and referred to as tailing, and may
A1.1. increase their retention. If this effect is caused by instrumental
% relative error 5 activity, the problem should be corrected. If the column is
100 3 ~concentration determined inherently active, a new column should be obtained. A measure
2 concentration known!/concentration known (2) of the tailing can be made and specified by applying a skewness
10.4 Report and use only those combinations of conditions calculation, which determines a ratio of the distances from the
from 10.2 that result in 3 % or less relative error. This is the peak apex perpendicular to the front and back of the peak at
splitter linearity range. 5 % of the peak height. See Annex A1, Fig. A1.3 for an
example of this calculation.
11. Column Evaluation skewness 5 B/A (6)
11.1 In order to establish that a column will perform as
11.5.1 This test method shall be made using the t-butanol
required, the following specifications shall be determined for
peak (0.5 %) in the analysis of the column performance
new column acceptability and are useful for periodic evalua-
mixture (7.5.5) at 35°C isothermal. The skewness ratio must be
tion of column deterioration. These specification determina-
greater than 1.0 and not more than 5.0.
tions can be made with or without a precolumn, since the
precolumn will have little effect on their values. See Annex A1,
12. Optimization of Instrument Operating Conditions
Fig. A1.1, for examples of these determinations. After perform-
ing the steps in Sections 9 and 10, analyze the column 12.1 The column temperature programming profile is de-
performance mixture (7.5.5) at 35°C isothermal, at least pendent upon the individual column characteristics. Table 2
through heptane. The remainder of the analysis may be lists the programming profile determined for a 100–m methyl
ignored, but the remaining components must be eluted from the silicone column with a precolumn as determined in Annex A1.
column prior to performing another analysis. Setting the The profile is determined by establishing satisfactory separa-
column temperature to 220°C for an additional 20 min will be tions for the sets of sample components listed in 12.3. It is not
sufficient. practical to expect complete separation of all components, so
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D 6730 – 01
the optimum for each column may contain some compromises,
also dependent upon any particular other separations deemed
important.
12.2 The use of retention indices to numerically express the
relative location of components among themselves and to
surrounding normal paraffins is a convenient convention. The
indices are also useful in providing a system of component
identification with complex analyses such as this. There are
several schemes for calculating retention indices, the first of
which is the Kovats method, developed to express the loga-
rithmic relationship of retention times of a homologous series
of compounds when chromatographed isothermally. While this
test method is not an isothermal column temperature proce- FIG. 3 i propanol/2-methyl/butene-1 and t butanol/2-
dure, it does contain isothermal steps and the longer tempera- methylbutene-2
ture program step is a slow rate. The use of the Kovats indices
provides a closer relationship to previous work in this field than success. The retention indices should be about 569.5, 571.5,
using the linear index format. and 574.0 for 2,3-dimethylbutane, MTBE, and
12.2.1 The formula for the calculation of Kovats retention 2-methylpentane, respectively. If the MTBE is too close to the
indices is: 2,3-DMC4, use a 9 min initial hold. If too close to the 2-MC5
RIi 5 100 3 ~n 1 ~log ~ti!– log ~tn!!/~log~tn11! 2 log~tn!!! (7) use an 11 min hold (Fig. 4).
12.3.4 1-methylcyclopentene/benzene—This is a key sepa-
where:
ration that is used to specify the column selectivity. Changing
RI = retention index,
n = carbon number of n-paraffin, column temperature produces only slight differences in this
ti = retention time of component, resolution (Fig. 5).
tn = retention time of preceding n-paraffin, and 12.3.4.1 The 50°C column temperature is held isothermal
tn+1 = retention time of next n-paraffin. until the elution of ethylbenzene. This is variable due to slight
12.3 The following examples show the key or critical differences in the column retention factor.
separations required for this analysis. Typical retention indices 12.3.5 2,3,3-trimethylpentane/toluene—This is a key sepa-
are given, and a description of the effect of instrumental ration that is used to specify the column selectivity. Column
conditions on the separation is provided. temperature has very little effect on this resolution, which is
12.3.1 i-butane/methanol and ethanol/3-methylbutene-1— controlled by the column selectivity for aromatics (Fig. 6).
The initial starting temperature of 5°C is dictated by these 12.3.6 p-xylene/2,3-dimethylheptane—This is a key separa-
separations. A lower starting temperature is not necessary and tion which limits the maximum length of the precolumn. If the
a higher temperature would effect the next set. The retention column selectivity is too great the aromatics are retained and
indices should be about 380 for methanol and 456.5 for ethanol this separation is not achieved. If this resolution is excessive
(Fig. 2). and the separation in 12.3.5 is insufficient, the precolumn
12.3.2 i-propanol/2-methylbutene-1 and t-butanol/2- should be lengthened slightly. Lowering the 50°C hold tem-
methylbutene-2—i-propanol will appear resolved between perature to 48°C will increase this separation (Fig. 7).
pentene-1 and 2-methyl-butene-1, t-butanol will appear re- 12.3.7 l17 (Unknown)/1,2-methylethylbenzene—The un-
solved between c-pentene-2 and 2-methylbutene-2. known isoparaffin (l17) appears to be a component of alkylate
12.3.2.1 Higher temperatures will move the alcohols into
the peaks ahead of them. At 35°C the alcohols will be located
ahead of the pentene-1 and c-pentene-2, respectively (Fig. 3).
12.3.3 2,3-dimethylbutane/methyl-t-butylether—This sepa-
ration is critical and the 5°C hold for 10 min determines its
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D 6730 – 01
13. Calibration
13.1 Qualitative—Determine the retention times of compo-
nents by analyzing known reference mixtures or samples under
identical conditions. Calculate retention indices from these
data using 12.2. Table A1.1 provides a listing of typical values
for this test method.
13.2 Quantitative, Hydrocarbons—Use theoretical response
factors for correction of the detector response of hydrocarbons
determined by this test method, unless response factors have
been determined experimentally. The response of an FID to
FIG. 6 2,3,3-trimethylpentane/toluene
hydrocarbons is determined by the ratio of the molecular
weight of the carbon in the analyte to the total molecular
weight of the analyte. If experimentally determined response
factors are to be used, they must be determined using known
purity individual standards and calculated using Practice
D 4626. The response factors, as listed in Table 3, are relative
to that calculated for heptane. Calculations are based on the
following equation:
FIG. 7 p-xylene/2,3-dimethylheptane
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D 6730 – 01
TABLE 3 Theoretical FID Relative Response Factors
Carbon No. Saturated Paraffins Unsaturated Paraffins Saturated Naphthenes Unsaturated Naphthenes Aromatics
1 1.1207 - - - -
2 1.0503 - - - -
3 1.0268 0.9799 - - -
4 1.0151 0.9799 - - -
5 1.0080 0.9799 0.9799 0.9517 -
6 1.0034 0.9799 0.9799 0.9564 0.9095
7 1.0000 0.9799 0.9799 0.9598 0.9195
8 0.9975 0.9799 0.9799 0.9623 0.9271
9 0.9955 0.9799 0.9799 0.9642 0.9329
10 0.9940 0.9799 0.9799 0.9658 0.9376
11 0.9927 0.9799 0.9799 0.9671 0.9415
12 0.9916 0.9799 0.9799 0.9681 0.9447
13 0.9907 0.9799 0.9799 0.9690 0.9474
14 0.9899 0.9799 0.9799 0.9698 0.9497
15 0.9893 0.9799 0.9799 0.9705 0.9517
Fi 5 ~~~~Caw 3 Cn! 1 ~Haw 3 Hn!!/Cn! 3 0.83905!/Caw! (8) 15.1.1 Proper component identification using retention in-
dices requires the use of windows surrounding each RI value in
where: order to account for the analysis to analysis variations. The
Fi = relative response factor for a hydrocarbon type
following windows have been found to provide satisfactory
group of a particular carbon number.
identification for this test method.
Caw = atomic weight of carbon 12.011,
Indices Window
Cn = number of carbon molecules in the group, 100 – 300 615
Haw = atomic weight of hydrogen, 1.008, 300 – 400 6 2.6
Hn = number of hydrogen molecules in the group, 400 – 500 6 1.5
0.83905 is the correction factor with heptane as 500 – 885 6 0.6
885 – 900 6 0.5
unity (1.0000), and > 900 6 0.6
0.7487 is used with methane as unity.
13.3 Quantitative, Oxygenates—Determine response fac- 15.2 Obtain the area for each peak. Multiply each peak area
tors for methanol, ethanol, and other oxygenated compounds by its appropriate response factor, taken from Table 2 or
experimentally. The principles in Practice D 4626 should be determined separately with standards, to obtain corrected peak
applied when determining these response factors. The response areas. Use a response factor of 1.000 for unknown peaks.
of the flame ionization detector for oxygenated compounds is 15.3 If required, determine the concentration of water in the
not directly (theoretically) related to mass concentration. A sample using Test Method D 1744, or an equivalent method.
study has indicated that the FID response is linear for the The total concentration of any other materials not determined
conditions of this test method (see Figs. 10 and 11). Each by this test method should also be obtained.
individual apparatus must be calibrated using gravimetrically 15.4 The corrected peak areas are normalized to 100 % or to
prepared standards, covering the sample concentration ranges 100 % minus the concentrations determined in 15.3.
expected and the scope of this test method. Standards used component % ~m/m! 5 corrected peak area
must comply with the requirements in Section 7. Figs. 10 and 3 ~100 2 % undetected!/total corrected peak area (9)
11 present calibration data for six oxygenates as determined in
a preliminary cooperative study report for calibration of this 16. Report
test method. Precision data will be prepared when more data 16.1 Report the concentration of each component as mass
becomes available. %, % (m/m), to the nearest 0.001 % (m/m).
16.2 These individual component data may be grouped by
14. Sample Analysis Procedure summing the concentration of compounds in each particular
14.1 Adjust the instrument operating variables to the values group type such as paraffin, isoparaffin, olefin, aromatic,
specified in Table 1 or as determined in Section 12. naphthene, oxygenates, and unknowns. Commercially avail-
14.2 Set the recorder or integration device, or both, for able software may be used to provide this function, as well as
accurate presentation and collection of the data. calculation of other properties of petroleum liquids. See the
14.3 Inject an appropriate size sample (as determined in caution in 5.3.
Section 10) into the injection port and start the analysis. Obtain
a chromatogram and a peak integration report. 17. Precision and Bias 12
17.1 Repeatability—The difference in two test results ob-
15. Calculation tained by the same operator with the same apparatus in a given
15.1 Identify each peak by matching retention indices (or laboratory under constant operating conditions on test samples
retention times) with those for known reference standards or
sample components. If a computing integrator is used, examine
the chromatographic data for proper peak integration. Examine 12
Supporting data is available from ASTM International Headquarters in the
the report to ensure peaks are properly identified. form of a research report. Request RR: D02–1518.
9
D 6730 – 01
10
D 6730 – 01
taken from the same laboratory sample should, in the long run, 17.3 Bias—No information can be presented on the bias of
in the normal and correct operation of the test method not the procedure in this test method for measuring hydrocarbon
exceed the values given in Table 4 and Table A1.3 for the concentrations because no material having an accepted refer-
gasoline components. ence value is available.
17.2 Reproducibility—The difference between two single
and independent measurements on test samples taken from the 18. Keywords
same bulk sample should, in the long run, in the normal and 18.1 detailed hydrocarbon analysis; DHA; gas chromotog-
correct operation of the test method, not exceed the values raphy; hydrocarbons; open tubular column; oxygenates;
given in Table 4 and Table A1.3 for the gasoline components. PIONA; PONA
11
D 6730 – 01
TABLE 4 Repeatability and Reproducibility of DHA Determinations
NOTE 1—The following is a partial list of precision data that has been prepared by statisticians of CS94 in accordance with RR: D2-1007, and
represents their best estimate of the cooperative study data. The complete precision data set appears in Annex A1., Table A1.3.
NOTE 2—For each analyte to qualify for a precision statement, it must be present in at least six samples, and detected by at least six laboratories, at
least once. The (repeatability standard deviation)/mean value for each analyte/sample combination must be less than or equal to 0.1, as per LOQ
requirements which, while not a standard, is what CS94 is recommending.
NOTE 3—
Legend:
rmin = lower 95 % confidence limit of rest,
rest = repeatability estimate in percent of concentration,
rmax = upper 95 % confidence limit of rest,
Rmin, Rest, Rmax = for reproducibility,
Cmin = lower concentration limit that rest, Rest is applicable, and
Cmax = upper concentration limit that rest, Rest is applicable.
Component Average RI rmin rest rmax Rmin Rest Rmax Cmin Cmax
n-butane 400.00 6.8 9.9 13.9 15.3 32.4 59.1 1.02 3.75
i-pentane 477.45 5.9 7.2 8.7 8.5 14.8 23.8 2.48 13.38
Pentene-1 490.83 5.2 7.5 10.5 9.7 13.8 19 0.06 0.43
n-pentane 500.00 5.2 6.5 8.1 7.1 10.4 14.8 1.06 3.49
Cyclopentane 566.84 3.8 4.9 6.2 7 10.1 14 0.07 0.59
2,3-dimethylbutane 569.24 2.9 3.2 3.5 5.1 8.5 13.1 0.7 1.91
n-hexane 600.00 2 2.4 2.9 3.6 5.1 6.9 0.33 2.52
Methylcyclopentane 625.86 2.2 2.6 3.1 4.5 6.4 8.7 0.37 2.35
1-methylcyclopentene 648.71 1.9 2.7 3.7 7.9 8.7 9.6 0.17 0.82
Benzene 649.92 2.6 3.6 4.8 5.5 9 13.7 0.17 1.58
Cyclohexane 657.81 2.7 3.7 4.9 8.2 14.8 24.3 0.07 0.9
2-methylhexane 667.61 1.6 2.2 2.9 5.1 6.1 7.2 0.39 1.09
2,2,4-trimethylpentane 688.48 2.4 3.2 4.1 7.4 11.4 16.7 0.1 11.26
n-heptane 700.00 2.5 3.4 4.5 7.7 10.8 14.7 0.21 1.06
Methylcyclohexane 717.89 2.8 3.4 4 4.1 5.9 8.2 0.11 1.2
2,3,4-trimethylpentane 746.83 2.3 3.8 6 5.8 7.8 10.3 0.08 4.26
Toluene 751.77 1.9 2.7 3.8 10.8 13.5 16.5 1.99 10.34
2-methylheptane 764.14 3.5 4.9 6.6 4.8 6.1 7.5 0.15 0.63
n-octane 800.00 2.2 3.6 5.5 6.5 15.7 30.9 0.14 0.75
Ethylbenzene 854.65 2.2 3.2 4.4 7.2 10.6 14.9 0.62 2.62
1,3-dimethylbenzene 864.22 2.6 3.3 4.2 9.7 12.5 15.7 1.55 6.66
3-methyloctane 880.24 5.1 8.5 13 8.7 15.5 24.9 0.07 0.29
n-nonane 900.20 3.9 6.4 9.8 8.6 10.3 12.2 0.06 0.34
n-propylbenzene 946.33 2.8 5 8.1 7.6 11.9 17.7 0.21 0.77
1,4-methylethylbenzene 956.22 3.5 5.3 7.7 5.1 7.7 11.1 0.32 1.19
1,3,5-trimethylbenzene 961.92 3.7 5.5 7.7 5.4 8.3 12.1 0.39 1.21
2-methylnonane 971.77 6.5 10.6 16.2 17.5 25.9 36.6 0.03 0.19
1,2,4-trimethylbenzene 983.40 4.2 5.7 7.5 7.8 10.6 13.9 1.19 4.32
n-decane 1000.20 7.5 9.2 11.1 12.1 17.9 25.3 0.03 0.25
1,2,3-trimethylbenzene 1006.88 3.8 5.8 8.5 7.2 8.5 10 0.28 0.96
n-undecane 1100.00 8.6 13.9 21 24.4 40 61.2 0.03 0.18
1,2,3,5-tetramethylbenzene 1108.79 6.4 7.8 9.3 10.2 13.9 18.3 0.21 0.51
Naphthalene 1168.01 6.1 8.5 11.3 12.9 16.9 21.5 0.13 0.4
n-dodecane 1200.00 12.2 16.7 22.1 20.2 32.9 50 0.01 0.11
2-methylnaphthalene 1282.57 7.6 11.1 15.4 17.5 22.3 28 0.05 0.5
12
D 6730 – 01
ANNEX
(Mandatory Information)
A1. PROCEDURE FOR ADJUSTING THE SELECTIVITY OF A DHA METHYL SILICONE OPEN TUBULAR COLUMN
A1.1 The successful application of this test method is A1.3 When necessary, a precolumn is added to the primary
highly dependent upon the selectivity of the column used. New 100–m column to adjust the column selectivity for aromatic
100 m 3 0.25 mm 0.5 µm methyl silicone open tubular fused compounds. Precolumns that have been used successfully are
silica columns will likely not have sufficient selectivity for variable lengths of 0.25 mm internal diameter fused silica open
aromatics to function properly. Critical to the successful tubular column containing a 1.0 µm film thickness of 5 %
analysis of reformulated and oxygenated spark engine motor phenyl methyl silicone. The film thickness is likely not critical,
fuels is column inertness and component selectivity. Inertness only the total amount of phase. Lengths ranging from 1 to more
of the primary 100–m column affects the retention and adsorp- than 3 m have been necessary to provide sufficient selectivity,
tion of the oxygenates such as alcohols and ethers, while depending on the initial selectivity of the methyl silicone
selectivity for the aromatic compounds is controlled by the column used. One metre of 1.0 µm precolumn is equivalent to
liquid phase. Until adequate commercial columns are available, a 100–m column with 0.5 µm of 0.1 % phenyl methyl silicone
it will be necessary to slightly increase the column selectivity, liquid phase.
which is accomplished by the addition of a short precolumn
containing a moderately selective liquid phase. A1.4 Figs. A1.5-A1.8 illustrate the resolution of the
methylcyclopentene-1 and benzene pair with a new column
A1.2 Prior to making any precolumn additions to the and one, two, and three metres of precolumn. The key segment
100–m methyl silicone capillary column, determine that the of the chromatogram is expanded to better illustrate the
main column meets the column specifications outlined in 6.4.1 resolution of this component pair.
and determined in Section 9. Section 9 describes the prelimi-
nary evaluation of the 100–m methyl silicone capillary column, A1.5 The preliminary evaluation of the 100–m column will
using a 35°C isothermal analysis to determine the basic column provide the user with information regarding the initial length of
characteristics of efficiency, retention factor, inertness, and precolumn with which to start the tuning process. Dependent
selectivity. Figs. A1.1-A1.3 provide examples of the column upon the methylcyclopentene-1 and benzene resolution, an
quality specification determinations. These determinations may initial precolumn of between 1 and 4 m is selected; which ever
also be made with a precolumn attached, since the precolumn provides a resolution greater than 1.2.
has little if any affect on the results. Fig. A1.4 illustrates that
the addition of different lengths of precolumn has negligible A1.6 The final tuning will consist of reducing the precol-
influence on the retention characteristics of oxygenated com- umn length, probably in increments of 0.25 m, until the proper
pounds. Poor peak shape and resolution of these oxygenates resolution is achieved between 2,3,3-trimethylpentane and
cannot be corrected by the addition of the precolumn. Tailing toluene, and 1,4-dimethylbenzene and 2,3-dimethylheptane;
peaks may also be the result of an active injector liner or using the actual analysis temperature conditions.
packing material, or both, in the injector liner. An increase in
retention of the oxygenates is likely due to column activity. The A1.7 Fig. A1.9 illustrates graphically the effect of different
relative position of the oxygenates to the hydrocarbons is lengths of precolumn, attached to the same 100–m column. The
dependent upon column temperature, thus a faulty column key component separations are shown. These analyses were
oven temperature control could also result in shifted peaks. made using the conditions given in Table 2. In this case, the use
13
D 6730 – 01
FIG. A1.2 Column Efficiency and Resolution Calculations (9.2 and 9.3)
of the 1.25–m precolumn provides the best compromise for the ent 100–m columns. The final precolumn length will provide
three key separations. adequate resolution of all three of the key separations.
A1.8 Fig. A1.10 illustrates the use of different lengths of A1.9 Figs. A1.11-A1.17 illustrate DHA analyses.
precolumn to achieve the specified selectivity for three differ-
14
D 6730 – 01
15
D 6730 – 01
FIG. A1.5 PONA-V Standard—Analysis through Benzene New DHA Column—Analyzed at 35°C Isothermal (Conditions in Accordance
with Table 2)
16
D 6730 – 01
FIG. A1.6 PONA-V Standard - Analysis through Benzene New DHA Column plus 1 m 3 0.25 mm 1 µm Precolumn Analyzed at 35 °C
Isothermal
17
D 6730 – 01
FIG. A1.7 PONA-V Standard - Analysis through Benzene New DHA Column plus 2 m 3 0.25 mm 1 µm Precolumn Analyzed at 35 °C
Isothermal
18
D 6730 – 01
FIG. A1.8 DHA Calibration Standard - Analysis through Benzene New DHA Column plus 3 m 3 0.25 mm 1 µm Precolumn Analyzed at 35
°C Isothermal
19
D 6730 – 01
FIG. A1.9 Key Separations - Effect of Different Precolumn Lengths Same Primary Column. Conditions in Accordance with Table 2 Top
to Bottom - 1.00 m, 1.25 m, 1.50 m, and 2.00 m Precolumn
20
D 6730 – 01
FIG. A1.10 Key Separations - Tuning of Different Columns Conditions in Accordance with Table 2
21
D 6730 – 01
22
D 6730 – 01
23
D 6730 – 01
24
D 6730 – 01
25
D 6730 – 01
26
D 6730 – 01
27
D 6730 – 01
28
D 6730 – 01
NOTE 1—These data consist of the current physical constants used in the cooperative study. The average RI are those accumulated in a ruggedness test
of the tuning process. The RFA and CCF gasoline data are the averages determined in the cooperative study. RFA is an industry average regular gasoline
and CCF is a California Certification Fuel (reformulated gasoline).
29
D 6730 – 01
30
D 6730 – 01
31
D 6730 – 01
32
D 6730 – 01
33
D 6730 – 01
34
D 6730 – 01
35
D 6730 – 01
36
D 6730 – 01
37
TABLE A1.2 Analyses of Naphtha, Reformate, Alkylate, and Other Refinery Streams
NOTE 1—These data consist of analyses of various refinery samples and the purpose for this table is to illustrate that the DHA test method is equally applicable to other refinery samples as well
as to the analysis of spark-ignition engine gasolines. This table presents the retention times and retention indices of the components covering a range of different concentrations as well as the actual
analyses.
File: DHA94108.D
File: DHA94098.D File: DHA94099.D File: DHA94101.D File: DHA94105.D Sample: ASTM Indolene Standard
Coopera- Sample: PONA-Va Sample: HFLA C-Matrix Sample: Platformate Sample: No. 1 Ref Naphtha
Component tive Study *NJ* Reference Mixture Auto/Oil C-Matrix Alkylate Auto/Oil C-Matrix Reformate ASTM No. 1 Reference Sample ASTM D02 Reference Standard
Average RI Min. Index Mass % Min. Index Mass % Min. Index Mass % Min. Index Mass% Min. Index Mass %
Methane 100.00
Ethylene 178.10
Ethane 200.00 6.70 201.5 0.033
Propylene 284.00
Propane 300.00 7.20 300.0 0.166
i-Butane 366.15 8.13 366.0 0.099 8.15 366.1 0.036 8.15 366.0 0.350
Methanol 378.82 8.42 378.6 0.362
Butene-1 390.72 8.74 390.6 0.087 8.75 390.6 0.007
Isobutylene 391.51 8.76 391.5 0.090
1,3-Butadiene 394.93 8.87 395.1 0.005
n-Butane 400.00 9.02 400.0 0.315 9.02 400.0 0.155 9.04 400.0 0.596 9.04 400.0 1.844
Vinyl acetylene 409.00
t-Butene-2 412.09 9.38 412.0 0.353 9.40 412.0 0.003 9.40 412.1 0.005
2,2-Dimethylpropane 415.10 9.46 414.6 0.005 9.49 414.7 0.024
c-Butene-2 427.74 9.92 427.5 0.438 9.94 427.6 0.004 9.95 427.6 0.012
1,2-Butadiene 450.00
Ethanol 455.33 11.13 454.8 6.914
D 6730 – 01
3-Methylbutene-1 460.84 11.43 460.5 0.418 11.46 460.6 0.005 11.47 460.6 0.021
38
O1 469.00
O2 474.00
i-Pentane 477.45 12.43 477.2 9.757 12.43 477.2 11.716 12.45 477.1 3.248 12.45 477.1 0.158 12.46 477.1 5.163
*Acetone 477.55
1,4-Pentadiene 481.18 12.70 481.1 0.004
Butyne-2 488.00
Pentene-1 490.83 13.40 490.8 0.951 13.43 490.9 0.007 13.44 490.9 0.041
i-Propanol 493.38 13.58 493.1 0.310
2-Methylbutene-1 496.66 13.87 496.7 1.811 13.90 496.8 0.029 13.91 496.8 0.099
n-Pentane 500.00 14.14 500.0 1.850 14.14 500.0 0.599 14.17 500.0 2.693 14.17 500.0 0.428 14.18 500.0 2.875
Isoprene 506.02 14.47 506.0 0.072
t-Pentene-2 510.56 14.74 510.7 1.641 14.77 510.9 0.022 14.78 510.8 0.090
3,3-Dimethylbutene-1 516.79 15.09 516.8 0.016
c-Pentene-2 519.53 15.27 519.7 0.888 15.30 519.9 0.012 15.31 519.8 0.055
t-Butanol 521.64 15.37 521.4 0.250
2-Methylbutene-2 524.92 15.61 525.2 1.980 15.61 525.3 0.005 15.64 525.3 0.060 15.65 525.2 0.165
1t,3-Pentadiene 527.97 15.81 528.3 0.042
3-Methylbutadiene-1,2 535.00
Cyclopentadiene 538.05 16.48 538.3 0.015
2,2-Dimethylbutane 540.54 16.64 540.7 0.087 16.64 540.6 0.005 16.67 540.6 0.185 16.67 540.6 0.067 16.68 540.6 0.330
1c,3-Pentadiene 541.90
O5 547.70
O6 549.70
Cyclopentene 557.21 17.91 557.5 0.157 17.94 557.5 0.020
n-Propanol 560.00
4-Methylpentene-1 562.02 18.31 562.5 0.062 18.35 562.5 0.011
3-Methylpentene-1 562.81 18.37 563.2 0.097 18.41 563.2 0.013
Cyclopentane 566.84 18.70 567.1 0.140 18.70 567.1 0.007 18.72 567.1 0.094 18.72 567.0 0.190 18.73 567.1 0.232
2,3-Dimethylbutane 569.24 18.91 569.6 0.611 18.90 569.5 2.601 18.93 569.6 0.346 18.94 569.6 0.228 18.95 569.6 1.522
Methyl-t-butylether 570.65 19.01 570.8 0.731
TABLE A1.2 Continued
File: DHA94108.D
File: DHA94098.D File: DHA94099.D File: DHA94101.D File: DHA94105.D Sample: ASTM Indolene Standard
Coopera- Sample: PONA-Va Sample: HFLA C-Matrix Sample: Platformate Sample: No. 1 Ref Naphtha
Component tive Study *NJ* Reference Mixture Auto/Oil C-Matrix Alkylate Auto/Oil C-Matrix Reformate ASTM No. 1 Reference Sample ASTM D02 Reference Standard
Average RI Min. Index Mass % Min. Index Mass % Min. Index Mass % Min. Index Mass% Min. Index Mass %
4-Methyl-c-pentene-2 571.00 19.09 571.4 0.008 19.10 571.4 0.018
2,3-Dimethylbutene-1 572.67 19.21 573.1 0.061 19.25 573.0 0.009
2-Methylpentane 573.70 19.30 574.1 2.213 19.29 573.9 0.754 19.32 574.1 1.878 19.33 574.0 1.857 19.34 574.0 2.536
4-Methyl-t-pentene-2 575.47 19.46 575.9 0.175 19.49 575.9 0.012 19.50 575.9 0.027
O8 578.00
2-Methyl-1,4- 579.00
pentadiene
1.5-Hexadiene 581.90
3-Methylpentane 585.52 20.38 585.7 1.450 20.37 585.6 0.356 20.40 585.7 1.441 20.41 585.7 1.332 20.42 585.7 1.831
2-Methylpentene-1 590.19 29.83 590.4 0.288 20.86 590.4 0.015 20.88 590.4 0.041
Hexene-1 591.06 20.92 591.2 0.157 20.95 591.3 0.005 20.97 591.2 0.020
O11 592.00
i-Butanol 593.50
1c/t,4-Hexadiene 597.14
2-Ethylbutene-1 598.95
n-Hexane 600.00 21.83 600.0 1.754 21.85 600.0 1.735 21.86 600.0 3.609 21.87 600.0 2.573
Diisopropylether 601.90
t-Hexene-3 602.83 22.06 602.9 0.323 22.09 603.0 0.010 22.11 603.0 0.035
c-Hexene-3 603.56 22.11 603.6 0.076 22.15 603.8 0.002
r-Hexene-2 605.44 22.27 605.5 0.436 22.30 605.6 0.014 22.32 605.5 0.049
2-Methylpentene-2 607.86 22.47 608.0 0.547 22.50 608.0 0.028 22.52 608.0 0.073
4-Methylcyclopentene
3-Methyl-c-pentene-2 610.54 22.68 610.6 0.308 22.71 610.7 0.018 22.73 610.6 0.041
39
3-Methylcyclopentene 611.61 22.76 611.5 0.040 22.81 611.5 0.007
O13 613.08 22.90 613.2 0.003
c-Hexene-2 614.67 23.04 614.8 0.250 23.07 614.8 0.008 23.08 614.8 0.028
O14 617.06 23.23 617.1 0.005
Ethyl-t-butylether 619.00
D 6730 – 01
3,3-Dimethylpentene-1 620.91 23.58 621.1 0.602 23.60 621.1 0.026 23.63 621.1 0.053
3-Methyl-t-pentene-2 622.11 23.70 622.4 0.009
2-Butanol 622.40
4,4-Dimethyl-t- 623.10
pentene-2
2,2-Dimethylpentane 624.17 23.86 624.3 0.053 23.86 624.0 0.006 23.88 624.2 0.118 23.89 624.2 0.104 23.91 624.2 0.174
Methylcyclopentane 625.86 23.99 625.7 1.057 24.02 625.7 0.310 24.03 625.7 2.226 24.04 625.7 0.982
Cyclic Diolefin or triole- 627.00
fin
2,4-Dimethylpentane 630.60 24.45 630.8 0.768 24.47 630.8 8.169 24.47 630.7 0.243 24.48 630.7 0.192 24.50 630.7 1.039
2,3,3- 631.00
Trimethylbutene-1
Cyclic Diolefin or triole- 632.90 24.67 633.1 0.013
fin
2,2,3-Trimethylbutane 634.86 24.83 634.9 0.046 24.83 634.7 0.057 24.86 634.9 0.010 24.87 634.8 0.027 24.88 634.8 0.091
636.38 25.00 636.6 0.010
Cyclic diolefin or triole- 638.30 25.16 638.4 0.011
fin
O17 641.97 25.52 642.0 0.006
3,4-Dimethylpentene-1 642.87 25.60 642.9 0.017
4,4-Dimethyl-c- 646.65 25.99 646.8 0.029 26.00 646.6 0.005 26.04 646.8 0.006
pentene-2
2,4-Dimethylpentene-1 647.67 26.06 647.6 0.021
Diolefin 647.70
1-Methylcyclopentene 648.71 26.18 648.7 0.328 26.24 648.7 0.042
TABLE A1.2 Continued
File: DHA94108.D
File: DHA94098.D File: DHA94099.D File: DHA94101.D File: DHA94105.D Sample: ASTM Indolene Standard
Coopera- Sample: PONA-Va Sample: HFLA C-Matrix Sample: Platformate Sample: No. 1 Ref Naphtha
Component tive Study *NJ* Reference Mixture Auto/Oil C-Matrix Alkylate Auto/Oil C-Matrix Reformate ASTM No. 1 Reference Sample ASTM D02 Reference Standard
Average RI Min. Index Mass % Min. Index Mass % Min. Index Mass % Min. Index Mass% Min. Index Mass %
Benzene 649.92 26.29 649.8 0.541 26.32 649.8 1.786 26.33 649.7 0.445 26.35 649.8 1.506
3-Ethylpentene-1 650.00
*n-Butanol 650.02
3-Methylhexene-1 650.95 26.42 651.0 0.038
2-Methyl-c-hexene-3 652.60 26.60 652.8 0.020 26.61 652.7 0.003
3,3-Dimethylpentane 654.43 26.77 654.4 0.049 26.77 654.2 0.009 26.80 654.5 0.109 26.81 654.4 0.073 26.82 654.4 0.161
5-Methylhexene-1 655.56 26.91 655.8 0.038 26.95 656.0 0.007 26.97 655.8 0.007
Cyclohexane 657.81 27.10 657.6 0.513 27.13 657.7 0.040 27.14 657.5 1.886 27.16 657.6 0.717
2-Methyl-t-hexene-3 661.03 27.49 661.2 0.078 27.51 661.2 0.006 27.54 661.2 0.011
Diolefin (hexadiene) 661.30
2-Ethyl-3- 662.60 27.65 662.7 0.014
methylbutene-1
4-Methylhexene-1 663.81 27.77 663.9 0.049 27.84 663.9 0.008
4-Methyl-t/c-hexene-2 666.23 28.05 666.4 0.138 28.08 666.4 0.012 28.09 666.2 0.020
2-Methylhexane 667.61 28.19 667.7 1.337 28.23 667.8 0.310 28.22 667.7 1.382 28.23 667.6 1.464 28.25 667.7 1.452
2,3-Dimethylpentane 668.84 28.32 668.8 1.179 28.37 669.0 13.267 28.35 668.8 0.484 28.37 668.8 0.539 28.38 668.8 1.229
5-Methyl-t-hexene-2 669.80
1,1-Dimethylcyclo- 671.25 28.58 671.1 0.085 28.61 671.1 0.048 28.62 671.0 0.508 28.64 671.1 0.130
pentane
t-Amylmethylether 672.48 28.71 672.3 0.200
Cyclohexene 673.69 28.85 673.5 0.050 28.91 673.4 0.009
3-Methylhexane 675.89 29.13 675.9 1.351 29.13 675.7 0.310 29.17 676.0 1.743 29.17 675.8 1.775 29.20 675.9 1.771
1,6-Heptadiene 677.40
40
3,4-Dimethyl-c- 679.46 29.55 679.5 0.049 29.59 679.6 0.005 29.61 679.5 0.012
pentene-2
5-Methyl-c-hexene-2 680.00
1c,3-Dimethylcyclo- 681.68 29.79 681.5 0.376 29.83 681.6 0.076 29.84 681.4 1.014 29.86 681.6 0.279
pentane
D 6730 – 01
1t,3-Dimethylcyclo- 684.37 30.12 684.2 0.331 30.15 684.3 0.081 30.16 684.1 0.950 30.18 684.2 0.255
pentane
3-Ethylpentane 685.98 30.34 686.0 0.189 30.36 686.0 0.009 30.34 685.8 0.175 30.36 685.7 0.169 30.38 685.9 0.183
1t,2-Dimethylcyclo- 687.07 30.44 686.9 0.359 30.48 686.9 0.097 30.49 686.8 1.785 30.51 686.9 0.446
pentane
2,2,4-Trimethylpentane 688.48 30.63 688.4 1.852 30.75 689.1 30.506 30.66 688.2 0.006 30.71 688.6 5.212
Heptene-1 688.60
2-Ethylpentene-1 689.58 30.78 689.6 0.071
1,5-Heptadiene 691.60 30.97 691.2 0.002 31.05 691.3 0.003
O25 692.89
3-Methyl-c-hexene-3 694.82 31.45 694.9 0.087 31.48 694.9 0.009 31.51 694.9 0.013
t-heptene-3 698.39 31.90 698.4 0.289 31.94 698.5 0.017 31.97 698.5 0.035
n-Heptane 700.00 32.11 700.0 1.810 32.14 700.0 1.304 32.17 700.0 4.808 32.18 700.0 1.914
c-Heptene-3 701.00
2-Methyl-2-hexene 701.30
3-Methyl-c-hexene-2 702.30 32.41 702.1 0.355 32.45 702.2 0.032 32.48 702.1 0.043
3-Methyl-t-hexene-3 702.99 32.55 703.1 0.130 32.59 703.1 0.012 32.62 703.1 0.016
t-Heptene-2 704.58 32.78 704.7 0.170 32.82 704.7 0.009 32.85 704.7 0.017
3-Ethylpentene-2 705.96 32.99 706.1 0.074 33.03 706.1 0.005 33.06 706.1 0.010
c-Heptene-2 708.82 33.40 708.8 0.252 33.44 708.9 0.020 33.48 708.9 0.041
3-Methyl-t-hexene-2 709.50
O28 710.53
2,3-Dimehylpentene-2 712.07 33.90 742.1 0.160 33.98 712.5 0.014 33.97 712.1 0.014
3-Ethylcyclopentene 713.22
O29 715.67 34.43 715.5 0.015
TABLE A1.2 Continued
File: DHA94108.D
File: DHA94098.D File: DHA94099.D File: DHA94101.D File: DHA94105.D Sample: ASTM Indolene Standard
Coopera- Sample: PONA-Va Sample: HFLA C-Matrix Sample: Platformate Sample: No. 1 Ref Naphtha
Component tive Study *NJ* Reference Mixture Auto/Oil C-Matrix Alkylate Auto/Oil C-Matrix Reformate ASTM No. 1 Reference Sample ASTM D02 Reference Standard
Average RI Min. Index Mass % Min. Index Mass % Min. Index Mass % Min. Index Mass% Min. Index Mass %
1c,2-Dimethylcyclo- 717.13 34.75 717.6 1.667 34.68 717.0 0.028
pentane
Methylcyclohexane 717.89 34.74 717.4 0.005 34.78 717.6 0.094 34.82 717.6 5.093 34.82 717.6 1.113
O30 719.00
2,2-Dimethylhexane 720.70 35.21 720.5 0.174 35.19 720.1 0.008 35.23 720.4 0.126 35.27 720.4 0.748 35.28 720.5 0.199
*1,1,3-Trimethyl- 720.72
cyclopentane
O32 721.00
O33 722.00
O34 723.00
O35 724.35 35.82 724.3 0.019
O36 726.26 36.14 726.2 0.014
Ethylcyclopentane 728.90 36.56 728.7 0.254 36.59 728.7 0.066 36.61 728.6 0.373 36.64 728.7 0.112
2,5-Dimethylhexane 730.05 36.78 730.0 0.386 36.80 729.9 2.941 36.82 730.1 0.211 36.84 729.9 0.258 36.87 730.1 1.326
2,2,3-Trimethylpentane 730.90
2,4-Dimethylhexane 731.84 37.08 731.8 0.480 37.10 731.7 3.098 37.12 731.9 0.387 37.14 731.7 0.295 37.17 731.9 0.849
733.53 37.37 733.5 0.015
O37 735.18
1c,2t,4-Trimethyl- 737.11 37.97 737.0 0.208 38.01 737.0 0.052 38.03 736.8 0.703 38.06 737.0 0.137
cyclopentane
3,3-Dimethylhexane 738.39 38.20 738.3 0.045 38.24 738.3 0.084 38.26 738.1 0.098 38.29 738.3 0.088
O38 740.43 38.60 740.5 0.008
742.18 38.91 742.2 0.015
41
743.20 39.07 743.1 0.019
1t,2c,3-Trimethyl- 744.21 39.24 744.0 0.196 39.28 744.1 0.035 39.30 743.9 0.871 39.33 744.1 0.156
cyclopentane
O39 745.34
2,3,4-Trimethylpentane 746.83 39.73 746.7 0.497 39.79 746.8 8.132 39.77 746.8 0.016 39.79 746.6 0.052 39.84 746.8 2.781
D 6730 – 01
l1 747.91 39.95 747.9 0.198 40.01 748.0 0.009 40.02 747.8 0.004
O40 749.37 40.21 749.3 0.060
2,3,3-Trimethylpentane 750.84 40.47 750.6 0.302 40.52 750.7 6.021 40.58 750.8 2.818
Toluene 751.77 40.64 751.5 2.306 40.78 752.1 12.895 40.70 751.4 1.930 40.77 751.8 7.664
O41 752.20
O42 753.63 41.03 753.6 0.031
O43 755.33 41.35 755.3 0.060
2,3-Dimethylhexane 757.87 41.86 757.8 0.417 41.86 757.6 2.284 41.92 758.0 0.263 41.94 757.8 0.472 41.96 757.9 0.856
2-Methyl-3- 759.04 42.08 759.0 0.065 42.09 758.8 0.099 42.14 759.1 0.045 42.15 758.8 0.136 42.19 759.1 0.062
ethylpentane
1,1,2-Trimethyl- 760.33 42.36 760.4 0.055
cyclopentane
O44 761.73 42.59 761.5 0.074
O45 762.20
O46 763.00
2-Methylheptane 764.14 43.12 764.1 1.092 43.10 763.8 0.075 43.17 764.2 0.836 43.20 764.0 2.228 43.22 764.1 0.785
*2-Ethylhexene-1 764.20
4-Methylheptane 765.62 43.42 765.6 0.359 43.41 765.3 0.022 43.47 765.7 0.433 43.50 765.5 0.524 43.52 765.6 0.305
3-Methyl-3- 766.62 43.64 766.7 0.056 43.60 766.2 0.229 43.67 766.6 0.070 43.69 766.4 0.064 43.71 766.6 0.100
ethylpentane
3,4-Dimethylhexane 767.18 43.71 767.0 0.061 43.72 766.8 0.267 43.78 767.2 0.073 43.80 766.9 0.096 43.83 767.1 0.107
1c,2c,4-Trimethyl- 768.95 44.23 769.3 0.024 44.27 769.2 0.100 44.28 769.3 0.028
cyclopentane
1c,3- 769.80 44.27 769.7 0.128
Dimethylcyclohexane
TABLE A1.2 Continued
File: DHA94108.D
File: DHA94098.D File: DHA94099.D File: DHA94101.D File: DHA94105.D Sample: ASTM Indolene Standard
Coopera- Sample: PONA-Va Sample: HFLA C-Matrix Sample: Platformate Sample: No. 1 Ref Naphtha
Component tive Study *NJ* Reference Mixture Auto/Oil C-Matrix Alkylate Auto/Oil C-Matrix Reformate ASTM No. 1 Reference Sample ASTM D02 Reference Standard
Average RI Min. Index Mass % Min. Index Mass % Min. Index Mass % Min. Index Mass% Min. Index Mass %
3-Methylheptane 771.78 44.71 771.7 0.873 44.70 771.5 0.064 44.76 771.8 1.057 44.79 771.6 1.166 44.81 771.8 0.718
1c,2t,3-Trimethyl- 772.98 44.92 772.7 0.734 44.92 772.5 0.009 44.98 772.9 0.299 45.00 772.6 1.845 45.02 772.8 0.412
cyclopentane
3-Ethylhexane 773.76 45.17 773.4 0.192
1t,4- 774.89 45.33 774.6 0.241 45.39 774.7 0.013 45.41 774.5 0.662 45.44 774.7 0.107
Dimethylcyclohexane
1,3-Octadiene 777.16 45.89 777.2 0.016
O48 778.50 46.16 777.9 0.002
1,1- 780.48 46.55 780.2 0.099 46.62 780.0 0.291 46.67 780.3 0.047
Dimethylcyclohexane
2,2,5-Trimethylhexane 782.93 47.16 782.9 0.274 47.19 782.8 3.951 47.22 783.0 0.010 47.25 782.8 0.030 47.28 783.0 1.175
3c-Ethylmethylcyclo- 784.35 47.44 784.1 0.199 47.50 784.2 0.037 47.52 784.0 0.216 47.56 784.2 0.054
pentane
2,6-Dimethylheptene-1 785.55 47.64 785.0 0.034
3t-Ethylmethylcyclo- 786.55 47.95 786.4 0.154 48.01 786.4 0.034 48.03 786.2 0.192 48.07 786.4 0.049
pentane
2t-Ethylmethylcyclo- 787.86 48.26 787.7 0.172 48.32 787.8 0.037 48.34 787.5 0.484 48.38 787.7 0.094
pentane
*Octene-1 787.87
1,1-Methylethylcyclo- 788.78 48.54 788.9 0.039 48.70 789.3 0.050 48.79 789.8 0.012 48.82 789.5 0.065 48.83 789.7 0.026
pentane
789.88 48.73 789.7 0.023
2,2,4-Trimethylhexane 790.75 49.00 790.8 0.053
42
1t,2- 792.77 49.41 792.6 0.314 49.47 792.7 0.021 49.49 792.4 0.902 49.52 792.6 0.141
Dimethylcyclohexane
t-Octene-4 794.21 49.83 794.3 0.075
3,5,5- 795.00
Trimethylhexene-1
D 6730 – 01
t-Octene-3 796.00
1c,2c,3-Trimethyl- 797.25 50.57 797.3 0.200 50.61 797.3 0.018 50.68 797.3 0.014
cyclopentane
1t,3- 798.80 50.91 798.7 0.051 50.94 798.3 0.031 50.97 798.5 0.006
Dimethylcyclohexane
n-Octane 800.00 51.23 800.0 1.978 51.27 800.0 0.837 51.36 800.0 5.227 51.34 800.0 1.159
1c,4- 801.05
Dimethylcyclohexane
3,3-Dimethylheptene-1 802.50
Octene-2 804.40 52.33 804.5 0.082
O50 805.50
l2 806.39 52.79 806.3 0.109 52.92 806.6 0.119 53.06 806.9 0.041
i-Propylcyclopentane 808.06 53.21 808.0 0.123 53.28 808.1 0.019 53.36 808.0 0.125 53.25 807.7 0.028
2,4,4-Trimethylhexane 808.50
O52 810.62 53.85 810.5 0.013
812.50 54.39 812.1 0.013
O53 813.47 54.60 813.4 0.044
N1 815.02 54.93 814.6 0.031 55.04 814.5 0.073 55.08 814.8 0.013
2,2,3,4- 816.45 55.35 816.2 0.014
Tetramethylpentane
2,3,4-Trimethylhexane 818.10 55.77 817.8 0.057 55.75 817.5 0.585 55.83 817.8 0.022 55.87 817.7 0.049 55.90 817.9 0.207
N2 819.93 56.21 819.4 0.063 56.25 819.4 0.014 56.30 819.3 0.067 56.33 819.4 0.017
820.85 56.45 820.3 0.016
N3 822.29 56.89 821.9 0.069 56.96 822.0 0.028 57.00 821.8 0.107 57.02 822.0 0.038
TABLE A1.2 Continued
File: DHA94108.D
File: DHA94098.D File: DHA94099.D File: DHA94101.D File: DHA94105.D Sample: ASTM Indolene Standard
Coopera- Sample: PONA-Va Sample: HFLA C-Matrix Sample: Platformate Sample: No. 1 Ref Naphtha
Component tive Study *NJ* Reference Mixture Auto/Oil C-Matrix Alkylate Auto/Oil C-Matrix Reformate ASTM No. 1 Reference Sample ASTM D02 Reference Standard
Average RI Min. Index Mass % Min. Index Mass % Min. Index Mass % Min. Index Mass% Min. Index Mass %
2,3,3- 824.74 57.55 824.3 0.024 57.58 824.0 0.003
Trimethylhexene-1
1c,2- 826.48 57.95 825.7 0.084 58.04 825.6 0.174 58.10 825.9 0.030
Dimethylcyclohexane
2,3,5-Trimethylhexane 827.51 58.23 826.8 0.172 58.20 826.4 0.116 58.28 826.8 0.094 58.35 826.7 0.304 58.37 826.8 0.095
2,2-Dimethylheptane 829.76 59.00 829.0 0.059
1,1,4-Trimethyl- 832.56 59.66 831.8 0.530 59.60 831.4 0.006 59.71 831.8 0.030 59.79 831.7 1.549 59.81 831.9 0.264
cyclohexane
N4 834.07 60.06 833.1 0.031 60.05 832.9 0.012 60.12 833.2 0.022 60.17 833.1 0.033 60.19 833.2 0.020
2,2,3-Trimethylhexane 834.96 60.42 834.4 0.263 60.40 834.1 0.056 60.49 834.5 0.059 60.55 834.3 0.862 60.57 834.5 0.183
2,4-Dimethylheptane 836.47 60.80 835.6 0.030 60.91 835.6 0.061
4,4-Dimethylheptane 838.68 61.43 837.8 0.323 61.41 837.5 0.020 61.55 837.7 1.205 61.58 837.9 0.175
Ethylcyclohexane 840.20
n-Propylcyclopentane 841.38 62.20 840.4 0.076 62.20 840.2 0.011 62.33 840.3 0.156 62.35 840.5 0.027
*1c,3c,5-Trimethyl- 841.40
cyclohexane
2,5-Dimethylheptane 842.63 62.68 841.9 0.326 62.66 841.7 0.192 62.74 842.0 0.179 62.80 841.9 0.421 62.84 842.1 0.212
3,3-Dimethylheptane 843.96 63.09 843.3 0.086 63.04 842.9 0.020 63.16 843.4 0.062 63.23 843.3 0.101 63.27 843.5 0.069
3,5-Dimethylheptane 845.02 63.30 843.9 0.038 63.46 844.0 0.100
2,6-Dimethylheptane 846.47 63.79 845.5 0.083 63.93 845.5 0.188 63.95 845.7 0.033
1,1,3-Trimethyl- 848.43 64.40 847.5 0.070 64.51 847.4 0.095 64.55 847.6 0.022
cyclohexane
2,4-Dimethylheptene-1 849.43
43
N7 850.89
N8 852.36 65.77 851.8 0.046 65.98 852.0 0.103 66.03 852.2 0.020
N10 853.04
Ethylbenzene 854.65 66.41 853.7 0.728 66.43 853.7 0.032 66.64 854.3 7.364 66.54 853.7 0.797 66.61 854.0 2.653
N11 854.70
D 6730 – 01
1c,2t,4t-Trimethyl- 856.34 66.91 855.3 0.222 66.90 855.1 0.049 67.04 855.3 0.580 67.08 855.5 0.106
cyclohexane
l3 858.51 67.63 857.5 0.032 67.75 857.4 0.042
2-Methyloctene-1 859.80 68.01 858.6 0.030
l4 860.89 68.51 860.1 0.033 68.61 859.9 0.030
2-Methyloctene-2 862.14 69.05 861.7 0.021
N12 863.00 69.25 862.3 0.016
N13 863.77
1,3-Dimethylbenzene 864.22 69.69 836.6 1.828 69.98 864.3 10.485 69.81 863.5 1.833 69.94 863.9 5.660
1,4-Dimethylbenzene 865.20 70.06 864.6 0.693 70.31 865.2 4.479 70.18 864.6 0.558 70.28 864.9 2.475
2,3-Dimethylheptane 866.02 70.36 865.5 0.261 70.32 865.3 0.127 70.47 865.4 0.560
3,4-Dimethylheptane 867.94 70.99 867.3 0.102 70.93 867.0 0.019 71.09 867.5 0.029 71.11 867.2 0.207 71.15 867.4 0.049
3,4-Dimethylheptane 868.78 71.30 868.2 0.042 71.23 867.9 0.021 71.38 868.3 0.029 71.36 868.0 0.065 71.48 868.4 0.032
N14 869.70 71.62 869.1 0.033 71.74 869.0 0.048 71.82 869.3 0.012
l5 870.95 72.11 870.5 0.106 72.23 870.7 0.053 72.21 870.3 0.131 72.28 870.6 0.051
4-Ethylheptane 872.73 72.83 872.5 0.025
4-Methyloctane 873.81 73.19 873.5 0.393 73.27 873.6 0.217 73.30 873.4 0.557 73.34 873.6 0.187
2-Methyloctane 874.76 73.55 874.4 0.560 73.53 874.3 0.006 73.63 874.6 0.215 73.66 874.4 0.822 73.69 874.5 0.222
N15 876.00 73.95 875.5 0.045 74.05 875.4 0.072 74.10 875.7 0.018
1c,2t,3-Trimethyl- 877.98 74.66 877.5 0.073 74.76 877.4 0.208 74.86 877.7 0.033
cyclohexane
3-Ethylheptane 879.11 75.19 878.9 0.135 75.24 878.9 0.063 75.29 878.8 0.206 75.32 878.9 0.066
3-Methyloctane 880.24 75.62 880.0 0.577 75.68 880.1 0.288 75.72 879.9 1.004 75.75 880.1 0.280
1c,2t,4c-Trimethyl- 881.67 76.05 881.2 0.061 76.23 881.6 0.042 76.17 881.1 0.090 76.40 881.8 0.124
cyclohexane
TABLE A1.2 Continued
File: DHA94108.D
File: DHA94098.D File: DHA94099.D File: DHA94101.D File: DHA94105.D Sample: ASTM Indolene Standard
Coopera- Sample: PONA-Va Sample: HFLA C-Matrix Sample: Platformate Sample: No. 1 Ref Naphtha
Component tive Study *NJ* Reference Mixture Auto/Oil C-Matrix Alkylate Auto/Oil C-Matrix Reformate ASTM No. 1 Reference Sample ASTM D02 Reference Standard
Average RI Min. Index Mass % Min. Index Mass % Min. Index Mass % Min. Index Mass% Min. Index Mass %
1,1,2-Trimethyl- 882.78 76.49 882.3 0.065 76.49 882.3 0.007 76.60 882.3 0.158 76.64 882.5 0.014
cyclohexane
1,2-Dimethylbenzene 883.47 76.83 883.2 1.011 76.86 883.2 0.062 76.98 883.5 5.364 76.92 883.1 0.970 76.99 883.4 3.212
884.87 77.43 884.8 0.022 77.56 884.8 0.021 77.48 884.6 0.003
l6 885.34 77.60 885.2 0.044 77.91 885.7 0.020 77.76 885.4 0.082
l7 886.38 77.99 886.2 0.054 77.97 886.1 0.296 78.08 886.1 0.022 78.13 886.3 0.141
N18 887.87
N19 888.36 78.70 888.1 0.323 78.62 887.8 0.011 78.80 888.0 0.990 78.83 888.1 0.172
Nonene-1 889.00 78.91 888.6 0.036 79.02 888.5 0.059
889.40 79.08 889.0 0.051 79.15 888.9 0.109
l8 889.78 79.32 889.6 0.112 79.41 889.5 0.332 79.45 889.7 0.047
N20 890.51 79.81 890.9 0.083 79.80 890.8 0.442 79.90 890.8 0.030 79.95 890.9 0.141
l9 891.29 80.20 891.8 0.033 80.26 891.6 0.057 80.30 891.8 0.011
i-Butylcyclopentane 892.11 80.54 892.7 0.091 80.70 892.7 0.116 80.69 892.8 0.024
N21 892.96
894.00 81.25 894.2 0.003
t-7-Methyloctene-3 895.10
N22 895.99 81.89 896.0 0.113 81.81 895.5 0.068
896.76 82.22 896.8 0.019
82.22 896.5 0.010
N23/c-nonene-2 897.24 82.46 897.4 0.070 82.57 897.3 0.083 82.61 897.5 0.016
t-Nonene-3 897.94
898.44 83.04 898.5 0.029
44
l10 898.70 82.93 898.5 0.081 83.01 898.7 0.242 83.26 899.0 0.140 83.15 898.8 0.110
899.19 83.17 899.1 0.026 83.33 899.4 0.007
n-Nonane 900.20 83.55 900.0 1.495 83.57 900.0 0.224 83.68 900.0 4.771 83.64 900.0 0.691
1,1-Methylethylcyclo- 901.39
hexane
D 6730 – 01
3,7-Dimethyloctene-1 903.40
N24 904.38 84.17 903.4 0.033 84.27 903.2 0.078
N25 905.50 84.43 904.9 0.108 85.54 904.7 0.056 84.58 905.1 0.013
t-2,2,5,5- 906.68
Tetramethylhexene-3
911.02 85.55 910.9 0.008 85.60 910.5 0.019
i-Propylbenzene 912.28 85.80 912.3 0.061 85.83 912.3 0.295 85.87 911.9 0.132 85.90 912.3 0.207
N26 913.43
N27 914.45 86.15 914.1 0.145 86.27 914.7 0.020 86.22 913.8 0.493 86.25 914.1 0.068
c-Nonene-3 915.00
l11 916.40 86.50 915.9 0.015
i-Propylcyclohexane 917.51 86.75 917.3 0.086 86.79 917.4 0.009 86.82 917.0 0.234 86.85 917.4 0.036
918.60 87.06 919.0 0.011 87.07 918.3 0.025
l12 921.30 87.53 921.4 0.098 87.51 921.2 0.130 87.57 921.4 0.013 87.60 921.1 0.228 87.64 921.5 0.093
2,2-Dimethyloctane 922.59 87.86 923.1 0.037 88.00 923.4 0.016
2,4-Dimethyloctane 924.39 88.13 924.6 0.135 88.11 924.4 0.017 88.16 924.5 0.029 88.20 924.2 0.274 88.21 924.5 0.042
N28 926.32 88.49 926.4 0.018 88.56 926.1 0.051
N29 927.99 88.75 927.8 0.037 88.82 927.5 0.101 88.85 927.8 0.014
2,6-Dimethyloctane 930.83 89.33 930.7 0.221 89.36 930.8 0.006 89.39 930.8 0.014 89.40 930.5 0.800 89.43 930.8 0.107
2,5-Dimethyloctane 932.66 89.75 932.9 0.144 89.72 932.7 0.021 89.78 932.8 0.038 89.81 932.6 0.245 89.84 932.9 0.050
934.50 90.51 936.7 0.053
n-Butylcyclopentane 936.13 90.38 936.1 0.078 90.44 935.8 0.212 90.48 936.2 0.028
l13 937.41 90.68 937.7 0.078 90.71 937.6 0.015 90.76 937.4 0.179 90.66 937.1 0.031
90.78 937.7 0.028
N30 938.04 90.83 938.4 0.059 90.84 938.2 0.016 90.93 938.3 0.125
TABLE A1.2 Continued
File: DHA94108.D
File: DHA94098.D File: DHA94099.D File: DHA94101.D File: DHA94105.D Sample: ASTM Indolene Standard
Coopera- Sample: PONA-Va Sample: HFLA C-Matrix Sample: Platformate Sample: No. 1 Ref Naphtha
Component tive Study *NJ* Reference Mixture Auto/Oil C-Matrix Alkylate Auto/Oil C-Matrix Reformate ASTM No. 1 Reference Sample ASTM D02 Reference Standard
Average RI Min. Index Mass % Min. Index Mass % Min. Index Mass % Min. Index Mass% Min. Index Mass %
l14 940.39 91.21 940.3 0.042 91.26 939.9 0.121
3,3-Dimethyloctane 942.30 91.66 942.5 0.295 91.62 942.3 0.011 91.68 942.4 0.039 91.73 942.3 1.121 91.75 942.6 0.158
N31 943.42 92.15 944.4 0.241
944.55 92.07 944.6 0.077 92.18 944.7 0.015
944.95 92.27 945.2 0.011
n-Propylbenzene 946.33 92.43 946.4 0.242 92.46 946.3 1.417 92.49 946.1 0.203 92.52 946.4 0.863
947.54 92.70 947.7 0.056 92.73 947.6 0.009 92.76 947.4 0.190 92.80 947.8 0.024
3,6-Dimethyloctane 948.31 92.85 948.5 0.051 92.89 948.4 0.007 92.92 948.2 0.069
3-Methyl-5- 949.41 93.08 949.6 0.125 93.15 949.4 0.669 93.18 949.6 0.063
ethylheptane
N32 951.22 93.39 951.1 0.058 93.48 951.0 0.158
1,3- 954.42 94.07 954.4 0.925 94.16 954.6 4.421 94.13 954.1 0.725 94.19 954.6 2.428
Methylethylbenzene
1,4- 956.22 94.44 956.2 0.359 94.51 956.2 1.972 94.50 955.9 0.300 94.55 956.3 1.063
Methylethylbenzene
N33 958.16 94.79 957.9 0.066 94.86 957.7 0.383 94.89 957.9 0.037
1,3,5-Trimethylbenzene 961.92 95.63 961.9 0.544 95.69 961.9 2.101 95.70 961.7 0.985 95.73 962.0 1.370
2,3-Dimethyloctane 961.99 95.72 962.2 0.019
l15 963.67 96.05 963.9 0.081 96.08 963.7 0.025 96.11 963.7 0.144 96.14 963.9 0.025
N34 964.76 96.20 964.6 0.024 96.27 964.4 0.158
l16 966.53
5-Methylnonane 967.89 96.93 968.1 0.159 96.96 967.9 0.023 97.00 967.9 0.262 97.03 968.1 0.033
l17 969.41 97.25 969.6 0.219 97.26 969.5 0.417 97.32 969.4 0.604
45
1,2- 970.33 97.39 970.2 0.306 97.43 970.1 1.356 97.45 970.0 0.218 97.49 970.3 1.308
Methylethylbenzene
2-Methylnonane 971.77 97.75 971.9 0.294 97.78 971.7 0.051 97.82 971.7 0.700 97.84 971.9 0.082
973.13 98.04 973.3 0.049 98.07 972.9 0.100
3-Ethyloctane 974.47 98.33 974.6 0.080 98.35 974.4 0.013 98.40 974.4 0.255 98.43 974.7 0.027
D 6730 – 01
46
l30 1024.82 107.68 1026.3 0.034 107.68 1025.7 0.029 107.77 1026.3 0.044
1025.70
1026.50
1,2-Methyl-i- 1027.73 107.90 1027.8 0.109 107.91 1027.4 0.013 107.96 1027.7 0.747 107.98 1027.8 0.035
propylbenzene
D 6730 – 01
3-Ethylnonane 1029.40 108.48 1031.8 0.063 108.55 1031.7 0.376 108.49 1031.4 0.217
1031.13 108.38 1030.9 0.044
N40 1032.29
1032.60 108.71 1032.9 0.105
l31 1033.20 108.67 1033.2 0.089 108.85 1033.8 0.115 108.82 1033.7 0.012
1035.50
l32 1036.92 109.17 1036.6 0.053 109.24 1036.5 0.242 109.27 1036.8 0.017
1038.53 109.45 1038.5 0.020 109.37 1037.7 0.014 109.50 1038.3 0.060 109.48 1038.2 0.101
1,3-Diethylbenzene 1039.97 109.63 1039.7 0.173 109.64 1039.4 0.477 109.73 1039.9 0.215 109.70 1039.7 0.143
1040.50 109.92 1041.5 0.030
1,3-Methyl-n- 1042.60 110.01 1042.4 0.257 110.04 1042.1 0.942 110.06 1042.2 0.260 110.06 1042.2 0.737
propylbenzene
l33 1044.35 110.31 1044.4 0.064 110.36 1044.2 0.329
1,4-Diethylbenzene 1045.25
1,4-Methyl-n- 1046.40 110.57 1046.2 0.152 110.60 1046.1 0.008 110.59 1045.9 0.596 110.62 1046.0 0.110 110.65 1046.2 0.264
propylbenzene
n-Butylbenzene 1047.48 110.72 1047.2 0.097 110.74 1046.9 0.224 110.77 1047.0 0.147 110.79 1047.2 0.080
1,3-Dimethyl-5- 1049.78 111.07 1049.6 0.249 111.10 1049.4 0.934 111.12 1049.4 0.184 111.15 1049.6 0.402
ethylbenzene
111.27 1050.4 0.042
1,2-Diethylbenzene 1051.72 111.32 1051.2 0.038 111.36 1051.1 0.070 111.42 1051.4 0.027
l34 1051.80 111.49 1052.4 0.040 111.55 1052.3 0.246
t-Decahydronaphthalene 1053.12 111.68 1053.1 0.023
N41 1054.60 111.83 1054.7 0.032 111.88 1054.6 0.093
1055.80 111.95 1055.5 0.013 112.05 1055.7 0.062
TABLE A1.2 Continued
File: DHA94108.D
File: DHA94098.D File: DHA94099.D File: DHA94101.D File: DHA94105.D Sample: ASTM Indolene Standard
Coopera- Sample: PONA-Va Sample: HFLA C-Matrix Sample: Platformate Sample: No. 1 Ref Naphtha
Component tive Study *NJ* Reference Mixture Auto/Oil C-Matrix Alkylate Auto/Oil C-Matrix Reformate ASTM No. 1 Reference Sample ASTM D02 Reference Standard
Average RI Min. Index Mass % Min. Index Mass % Min. Index Mass % Min. Index Mass% Min. Index Mass %
1,2-Methyl-n- 1057.87 112.26 1057.5 0.123 112.28 1057.3 0.277 112.31 1057.4 0.176 112.34 1057.6 0.139
propylbenzene
l35 1058.87 112.46 1058.9 0.018 112.50 1058.7 0.047
112.83 1061.1 0.038
l36 1060.15 112.59 1059.8 0.014 112.66 1059.8 0.036
l37 1062.62 113.03 1062.7 0.091 113.10 1062.9 0.007 113.05 1062.5 0.009 113.08 1062.6 0.199 112.93 1061.5 0.400
1063.96 113.20 1063.3 0.059
l38 1065.53 113.47 1065.6 0.090 113.47 1065.4 0.006 113.49 1065.4 0.009 113.52 1065.5 0.231 113.57 1065.8 0.037
113.67 1066.5 0.052
1,4,Dimethyl-2- 1068.05 113.80 1067.7 0.185 113.82 1067.6 0.502 113.85 1067.7 0.108 113.87 1067.8 0.229
ethylbenzene
A3 1068.90
1,3-Dimethyl-4- 1069.53 114.01 1069.2 0.316 114.05 1069.2 0.530 114.05 1069.0 0.380 114.11 1069.3 0.230
ethylbenzene
l39 1071.12 114.32 1071.2 0.033 114.36 1071.0 0.061 114.27 1070.4 0.202
1072.49 114.17 1070.0 0.025
l40 1074.39 114.72 1073.8 0.147 114.74 1073.7 0.050 114.80 1073.8 0.022
1,2-Dimethyl-4- 1075.25 114.89 1074.9 0.360 114.92 1074.9 0.886 114.93 1074.8 0.388 114.98 1075.0 0.419
ethylbenzene
1076.00 115.06 1075.8 0.005
1077.91 115.28 1077.5 0.017 115.30 1077.2 0.080
l41 1079.65 116.65 1079.4 0.064
1,3-Dimethyl-2- 1080.68 115.72 1080.3 0.053 115.74 1080.2 0.045 115.77 1080.2 0.036 115.82 1080.5 0.040
47
ethylbenzene
l42 1081.60 115.94 1081.7 0.012 115.90 1081.3 0.015 116.07 1082.2 0.035 116.00 1081.7 0.168
l43 1084.18 116.32 1084.1 0.017 116.35 1084.0 0.044
1085.30 116.44 1084.9 0.016 116.49 1084.9 0.055
1086.54 116.71 1086.3 0.072 116.70 1086.2 0.013
D 6730 – 01
48
1,2-Di-i-propylbenzene 1153.16 125.11 1152.8 0.042 125.13 1152.8 0.071 125.18 1152.9 0.015
1154.09 125.23 1153.8 0.056 125.24 1153.8 0.066 125.29 1153.7 0.012
1157.64 125.65 1157.2 0.045 125.67 1157.3 0.068 125.72 1157.3 0.021
1,4-Di-i-propylbenzene 1159.52 125.91 1159.4 0.110 125.90 1159.2 0.085 125.95 1159.1 0.017
1161.30 126.29 1161.8 0.013
D 6730 – 01
49
1257.39 137.11 1257.6 0.029
1259.54 137.25 1258.9 0.050 137.25 1258.7 0.021
1262.15 137.61 1262.2 0.041
1266.71 138.08 1266.5 0.062
1269.02 138.31 1268.6 0.030 138.30 1268.3 0.015
D 6730 – 01
NOTE 1—The following data has been prepared by statisticians of CS94 in accordance with RR: D02-1007, and represents their best estimate of the
cooperative study data. Not all of the data qualified for this evaluation since:
(a) For each analyte to qualify for a precision statement, it must be present in at least six samples, and detected by at least six laboratories, at least once.
(b) The (repeatability standard deviation)/mean value for each analyte/sample combination must be less than or equal to 0.1, in accordance with LOQ
requirements which, while not a standard, is what CS94 is recommending.
NOTE 2—
Legend:
rmin = lower 95 % confidence limit of rest,
rest = repeatability estimate in percent of concentration,
rmax = upper 95 % confidence limit of rest,
Rmin, Rest, Rmax = for reproducibility,
Cmin = lower concentration limit that rest, Rest is applicable, and
Cmax = upper concentration limit that rest, Rest is applicable.
Component Average RI rmin rest rmax Rmin Rest Rmax Cmin Cmax
i-Butane 366.15 5.6 10.1 16.4 22.8 46.1 81.5 0.06 0.38
Butene-1 390.72 6.4 11.1 17.6 31.2 64.5 115.8 0.01 0.14
n-Butane 400.00 6.8 9.9 13.9 15.3 32.4 59.1 1.02 3.75
2,2-Dimethylpropane 415.10 3.3 8.8 18.6 32.1 50.1 73.7 0.01 0.02
i-Pentane 477.45 5.9 7.2 8.7 8.5 14.8 23.8 2.48 13.38
Pentene-1 490.83 5.2 7.5 10.5 9.7 13.8 19.0 0.06 0.43
2-Methylbutene-1 496.66 4.9 6.9 9.4 8.3 12.9 19.0 0.14 0.86
n-Pentane 500.00 5.2 6.5 8.1 7.1 10.4 14.8 1.06 3.49
t-Pentene-2 510.56 4.5 6.5 9.0 7.2 10.3 14.4 0.28 1.16
c-Pentene-2 519.53 4.7 6.3 8.1 7.6 13.2 20.9 0.16 0.63
2-Methylbutene-2 524.92 4.3 6.0 8.1 7.8 11.4 15.9 0.50 1.85
1t,3-Pentadiene 527.97 6.7 14.0 25.3 17.0 25.3 35.9 0.01 0.06
2,2-Dimethylbutane 540.54 3.1 4.7 6.8 6.4 9.9 14.6 0.08 2.18
Cyclopentene 557.21 4.0 5.8 8.1 7.6 10.5 13.9 0.07 0.27
4-Methylpentene-1 562.02 2.7 4.2 6.1 8.9 11.3 14.0 0.02 0.09
3-Methylpentene-1 562.81 3.5 5.0 6.9 6.1 8.8 12.0 0.03 0.12
Cyclopentane 566.84 3.8 4.9 6.2 7.0 10.1 14.0 0.07 0.59
2,3-Dimethylbutane 569.24 2.9 3.2 3.5 5.1 8.5 13.1 0.70 1.91
2-Methylpentane 573.70 2.5 2.9 3.4 5.1 6.6 8.4 1.06 5.80
4-Methyl-t-pentene-2 575.47 6.5 8.7 11.3 18.1 28.0 41.1 0.08 0.28
3-Methylpentane 585.52 2.6 2.9 3.2 4.0 5.6 7.5 0.60 2.50
2-Methylpentene-1 590.19 2.3 2.7 3.2 3.8 5.4 7.4 0.11 0.45
Hexene-1 591.06 3.1 4.2 5.5 5.9 8.2 10.9 0.06 0.26
n-Hexane 600.00 2.0 2.4 2.9 3.6 5.1 6.9 0.33 2.52
t-Hexene-3 602.83 1.9 3.2 4.9 7.4 11.8 17.7 0.08 0.35
t-Hexene-2 605.44 2.5 2.8 3.2 4.5 6.4 8.9 0.16 0.71
2-Methylpentene-2 607.86 2.4 3.0 3.8 6.1 13.1 24.1 0.22 0.97
3-Methyl-c-pentene-2 610.54 2.1 2.5 2.9 5.3 6.9 8.7 0.11 0.48
3-Methylcyclopentene 611.61 3.0 4.6 6.8 10.1 12.8 15.9 0.02 0.10
c-Hexene-2 614.67 2.6 3.3 4.1 4.8 5.4 6.1 0.09 0.40
3,3-Dimethylpentene-1 620.91 1.9 2.5 3.1 4.3 5.7 7.5 0.17 0.75
2,2-Dimethylpentane 624.17 3.3 4.3 5.5 4.4 8.2 13.7 0.01 0.09
Methylcyclopentane 625.86 2.2 2.6 3.1 4.5 6.4 8.7 0.37 2.35
2.4-Dimethylpentane 630.60 1.6 2.5 3.8 4.2 5.3 6.6 0.20 1.94
2,2,3-Trimethylbutane 634.86 3.2 7.1 13.1 12.5 20.4 31.1 0.02 0.08
3,4-Dimethylpentene-1 642.87 5.5 14.7 30.6 9.7 22.3 43.0 0.01 0.03
4,4-Dimethyl-c-pentene-2 646.65 3.8 5.6 8.0 6.1 11.0 17.9 0.01 0.11
2,4-Dimethylpentene-1 647.67 3.8 6.7 10.8 11.9 13.5 15.3 0.01 0.04
1-Methylcyclopentene 648.71 1.9 2.7 3.7 7.9 8.7 9.6 0.17 0.82
Benzene 649.92 2.6 3.6 4.8 5.5 9.0 13.7 0.17 1.58
5-Methylhexene-1 655.56 5.3 7.5 10.1 18.0 30.4 47.6 0.01 0.22
Cyclohexane 657.81 2.7 3.7 4.9 8.2 14.8 24.3 0.07 0.90
2-Methyl-t-hexene-3 661.03 3.2 6.3 11.0 16.8 23.4 31.6 0.03 0.14
2-Ethyl-3-Methylbutene-1 662.60 4.1 8.9 16.5 89.5 117.0 149.7 0.01 0.04
4-Methylhexene-1 663.81 2.5 4.5 7.2 11.7 14.7 18.3 0.02 0.09
4-Methyl-t/c-hexene-2 666.23 2.1 3.2 4.7 5.4 7.3 9.5 0.05 0.28
2-Methylhexane 667.61 1.6 2.2 2.9 5.1 6.1 7.2 0.39 1.09
2,3-Dimethylpentane 668.84 1.6 2.3 3.2 5.4 6.4 7.5 0.33 3.16
3-Methylhexane 675.89 1.9 2.8 4.0 4.7 5.6 6.7 0.37 1.08
3-4-Dimethyl-c-pentene-2 679.46 3.6 5.9 9.1 11.6 23.4 41.2 0.02 0.14
1c,3-dimethylcyclopentane 681.68 1.7 2.7 4.0 5.4 7.5 10.1 0.11 0.56
1t,3-Dimethylcyclopentane 684.37 1.7 2.8 4.4 5.4 7.7 10.5 0.08 0.48
3-Ethylpentane 685.98 3.1 3.7 4.3 5.6 8.3 11.9 0.08 0.26
2,2,4-Trimethylpentane 688.48 2.4 3.2 4.1 7.4 11.4 16.7 0.10 11.26
50
D 6730 – 01
51
D 6730 – 01
52
D 6730 – 01
A1.10 Tables A1.4-A1.9 show comparisons between this cluded only spark ignition fuels and different results may be
test method and other methods for several compound types. obtained with pure blending components.
Multidimensional PIONA is included since it tends to give
reasonable peak compound type groupings for total olefins,
total paraffins, and total naphthenes. The differences for ben-
zene and toluene among the indicated methods are well within
the reproducibilities of the methods. The sample numbers refer
to the interlaboratory cooperative study samples. It should be
noted that the interlaboratory cooperative study samples in-
53
D 6730 – 01
TABLE A1.5 Toluene
Toluene (wt %)
Sample D 5580 D 6730
2 4.3 4.5
6 2.1 2.0
8 10.1 10.3
10 5.0 5.2
13 3.3 3.3
14 4.4 4.7
54
D 6730 – 01
TABLE A1.9 Total Paraffins and Total Naphthenes
Total Paraffins (wt %) Total Naphthenes (wt %)
Sample PIONAA D 6730 PIONAA D 6730
8 35.6 38.0 2.2 2.7
10 41.1 45.5 5.6 6.5
13 42.6 46.0 1.3 2.1
14 34.1 41.3 5.9 9.3
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 methods. 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, October 1982. “Detailed Characterization of Petroleum Products with Capil-
X1.1.2 Johansen, N.G., Ettre, L.S., and Miller, R.L., “ lary GC Analyzers,” Analusis, 23, 1995, pp. 481-483.
Quantitative Analysis of Hydrocarbons by Structural Group X1.1.7 Canadian General Standards Board: CAN/CGSB
Type in Gasolines and Distillates. Part 1,” Journal of Chroma-
–3.0, No. 14.3-94, “Test Method for Individual Hydrocarbon
tography, 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 “Determination of Hydrocarbon Type Contents in Motor Gaso-
1993. lines from Detailed Analysis Capillary Gas Chromatography.”
X1.1.4 Schubert, A.J., and Johansen, N.J., “Cooperative
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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55