Designation: D7169 − 16

Standard Test Method for

Boiling Point Distribution of Samples with Residues Such
as Crude Oils and Atmospheric and Vacuum Residues by
High Temperature Gas Chromatography1
This standard is issued under the fixed designation D7169; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope* 1.5 This test method is not applicable for the analysis of
1.1 This test method covers the determination of the boiling materials containing a heterogeneous component such as
point distribution and cut point intervals of crude oils and polyesters and polyolefins.
residues by using high temperature gas chromatography. The 1.6 The values stated in inch-pound units are to be regarded
amount of residue (or sample recovery) is determined using an as standard. The values given in parentheses are mathematical
external standard. conversions to SI units that are provided for information only
1.2 This test method extends the applicability of simulated and are not considered standard.
distillation to samples that do not elute completely from the 1.7 This standard does not purport to address all of the
chromatographic system. This test method is used to determine safety concerns, if any, associated with its use. It is the
the boiling point distribution through a temperature of 720 °C. responsibility of the user of this standard to establish appro-
This temperature corresponds to the elution of n-C100. priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. Specific warning
1.3 This test method is used for the determination of boiling
statements are given in Section 8.
point distribution of crude oils. This test method uses capillary
columns with thin films, which results in the incomplete
2. Referenced Documents
separation of C4-C8 in the presence of large amounts of carbon
disulfide, and thus yields an unreliable boiling point distribu- 2.1 ASTM Standards:2
tion corresponding to this elution interval. In addition, quench- D2887 Test Method for Boiling Range Distribution of Pe-
ing of the response of the detector employed to hydrocarbons troleum Fractions by Gas Chromatography
eluting during carbon disulfide elution, results in unreliable D2892 Test Method for Distillation of Crude Petroleum
quantitative analysis of the boiling distribution in the C4-C8 (15-Theoretical Plate Column)
region. Since the detector does not quantitatively measure the D4057 Practice for Manual Sampling of Petroleum and
carbon disulfide, its subtraction from the sample using a Petroleum Products
solvent-only injection and corrections to this region via D6352 Test Method for Boiling Range Distribution of Pe-
quenching factors, results in an approximate determination of troleum Distillates in Boiling Range from 174 °C to
the net chromatographic area. A separate, higher resolution gas 700 °C by Gas Chromatography
chromatograph (GC) analysis of the light end portion of the D7500 Test Method for Determination of Boiling Range
sample may be necessary in order to obtain a more accurate Distribution of Distillates and Lubricating Base Oils—in
description of the boiling point curve in the interval in question Boiling Range from 100 °C to 735 °C by Gas Chroma-
as described in Test Method D7900 (see Appendix X1). tography
D7900 Test Method for Determination of Light Hydrocar-
1.4 This test method is also designed to obtain the boiling
bons in Stabilized Crude Oils by Gas Chromatography
point distribution of other incompletely eluting samples such as
E594 Practice for Testing Flame Ionization Detectors Used
atmospheric residues, vacuum residues, etc., that are charac-
in Gas or Supercritical Fluid Chromatography
terized by the fact that the sample components are resolved
E1510 Practice for Installing Fused Silica Open Tubular
from the solvent.
Capillary Columns in Gas Chromatographs
1
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
2
Subcommittee D02.04.0H on Chromatographic Distribution Methods. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Oct. 15, 2016. Published November 2016. Originally contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
approved in 2005. Last previous editing approved in 2011 as D7169 – 11. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D7169-16. the ASTM website.

*A Summary of Changes section appears at the end of this standard

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

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 D7169 − 16
3. Terminology 3.1.14.1 Discussion—%Recovery is calculated from the
3.1 Definitions of Terms Specific to This Standard: sample area (ASMP), the response factor (RF), the sample mass,
3.1.1 cut point interval, n—the mass % obtained between (MSMP), and the solvent mass (MSLSMP) used in sample
two selected temperatures of the interval. dissolution.
3.1.2 data acquisition rate, n—the speed of conversion of 3.1.15 %recovery threshold (Rt) , n—if the %recovery falls
the analog signal to a digital signal, expressed in Hz (cycles/ above a preset limit, the sample is considered fully eluted and
second). its recovery is assumed to be 100 %.
3.1.3 final boiling point (FBP), n—the temperature, for fully 3.1.15.1 Discussion—If the %recovery values found for
eluting samples (recovery = 100 %), at which 99.5 % of the duplicate analyses of a nearly completely eluting sample are
sample is eluted. 99.6 % and 101.2 %, the %recovery threshold (Rt) may be set
to 99.6 % and thus either of these results may be considered as
3.1.4 final elution time (FEt), n—the retention time of the
component of the reference time standard sample that elutes at fully eluted and set to 100 %.
the end of the temperature ramp of the oven. 3.2 Symbols:
3.1.5 final elution temperature (FET), n—the boiling point 3.2.1 ASMP—net area of the sample
of the normal paraffin that elutes at the time when the oven 3.2.2 ASTD—net area of the response factor standard
reaches its final temperature.
3.2.3 MSL—mass of solvent used in preparing sample solu-
3.1.6 initial boiling point (IBP), n—the temperature corre-
tion
sponding to an accumulated 0.5 % of the total area of the eluted
sample after correcting for the percent of sample recovery. 3.2.4 MSLSTD—mass of solvent used in preparing the re-
3.1.7 quenching factor (QF), n—a number that corrects for sponse factor standard solution
the diminished response due to the solvent profile co-eluting 3.2.5 MSMP—sample mass used in sample preparation
with sample components.
3.2.6 MSTD—mass of the standard used in preparing the
3.1.7.1 Discussion—Data acquired during the quenching
response factor solution
interval (QI) shall be corrected by applying the quenching
factor.
4. Summary of Test Method
3.1.8 quenching interval (QI), n—the time interval of the
start and end of elution of the CS2 used as a solvent. 4.1 This is a gas chromatographic method utilizing an inlet
3.1.8.1 Discussion—Sample components that elute during and a capillary column, both of which are subject to a
this time interval shall be corrected by a factor due to their temperature program. A flame ionization detector is used as a
diminished response resulting from the co-elution of the transducer that converts mass to an electrical signal A data
relatively large amount of solvent present in the sample with acquisition system operating in the slice mode and chromatog-
the light sample components. raphy software is used to accumulate the electronic signal. A
3.1.9 residue (R), n—the mass % of the sample that has not retention time calibration mixture is used to develop a retention
eluted at the temperature of calculation. time versus boiling point curve. A solution of the Reference Oil
3.1.9.1 Discussion—Residue is calculated from the %recov- 5010 or a gravimetric blend, which fully elutes from the
ery. column under the conditions of the test method and whose
boiling point distribution have been characterized in Test
3.1.10 response factor (RF), n—the factor used in order to Method D6352 or D7500, is used to determine the detector
calculate the %recovery of the sample. response factor. Solvent injections are made, and the resulting
3.1.10.1 Discussion—The response factor is determined signal is subtracted from both the response factor standard and
from the net area of the standard (ASTD), mass of standard the sample chromatogram. Finally, the sample solution is
(MSTD), and mass of solvent (MSLSTD) used in the solution of injected and with the use of the response factor, the amount of
the standard. A fully eluting sample, such as Reference Oil
sample recovered is calculated. After converting the retention
5010, is used in obtaining the response factor.
times of the sample slices to temperature, the boiling point
3.1.11 sample area obtained (ASMP) , n—the net chromato- distribution can be calculated up to the recovered amount.
graphic area (after baseline subtraction) obtained for the
sample at the final elution time or temperature. 5. Significance and Use
3.1.12 slice, n—the reciprocal of the data acquisition rate;
5.1 The determination of the boiling point distribution of
the time interval used to accumulate data, expressed in sec-
crude oils and vacuum residues, as well as other petroleum
onds.
fractions, yields important information for refinery operation.
3.1.12.1 Discussion—Normally 0.1 s is used. In cases where
These boiling point distributions provide information as to the
sample elutes immediately after injection, 0.05 s is used.
potential mass percent yield of products. This test method may
3.1.13 start elution temperature (SET), n—the temperature provide useful information that can aid in establishing opera-
at which the first amount of hydrocarbon is detected by the tional conditions in the refinery. Knowledge of the amount of
flame ionization detector above a predetermined threshold. residue produced is important in determining the economics of
3.1.14 %recovery (RC), n—percentage of the sample eluted. the refining process.

2
 D7169 − 16
6. Apparatus The latter should preferably have a visible indicator in order to
6.1 Gas Chromatograph—A gas chromatograph provided assess the remaining capacity of the oxygen trap.
with a cryogenic valve for cooling the oven to sub ambient 6.3 Data System—A data system composed of a computer
temperatures is required. Typical conditions of operating the and software for data acquisition, which digitizes the detector
Gas Chromatograph are given in Table 1. It shall also have the signal, is recommended. Some instrumentation digitizes the
following components: signal at the electrometer board in order to reduce noise. The
6.1.1 Flame Ionization Detector (FID)—A flame ionization data system is used at acquisition rates of about 10 Hz, which
detector capable of maintaining a temperature 5 °C to 10 °C correspond to slices of 0.1 s. This rate of data acquisition is
higher than the highest column temperature. The flame ioniza- necessary to obtain a minimum number of slices void of
tion detector should possess a jet orifice of about 0.018 in. sample or solvent elution immediately after injection. Data
(0.45 mm) in order to delay the plugging of the orifice due to acquisition systems facilitate the inspection of the baseline
column bleed. The FID should possess a sensitivity of under high magnification and allow the inspection of the
0.005 coulombs ⁄g (see Practice E594) and should have a linear retention time calibration mixture chromatogram. Retention
range of 106. time shifts can be measured. Overlaying chromatograms is also
6.1.2 Inlet—Either a temperature programmable inlet with a possible to ascertain similar signal amplitude.
glass liner or a cool-on-column inlet can be used. The inlet 6.4 Automatic Sample Injector—It is mandatory to use an
shall be capable of operating in a temperature-programmed auto sampler since the external standard technique used in this
mode from 50 °C to the final temperature of the oven. It is analysis requires identical volumes for all injections.
important that the temperature of the inlet, at any time during Additionally, small volumes (0.1 µL to 0.2 µL) shall be injected
the analysis, be either equal to or greater than the oven in a reproducible manner. Syringes of 5 µL to 10 µL having
temperature. With the use of either inlet, frequent replacement needle gauges of size 23 to 26 are to be used.
of the liner or removal of a section of the column may be
required due to accumulation of non-volatile sample compo- 6.5 Carrier Gas Control—The gas chromatograph shall be
nents. It is important that a leak free seal be reestablished after operated under constant flow conditions. The flow rate at the
replacement of the liner or the removal of a small section of the beginning of the oven temperature program shall not differ by
column. more than 1 % from the flow measured at the final oven
temperature. Electronic pneumatic control is highly recom-
6.2 Carrier Gas Purification System—Gas purifiers are used mended.
in order to remove traces of oxygen as well as moisture and
other impurities present in the carrier gas. The purification 7. Column and Column Performance Criteria
system should contain a hydrocarbon trap and an oxygen trap. 7.1 A 100 % bonded polydimethylsiloxane column having a
nominal inside diameter of 0.5 mm and a film thickness of
0.09 µm to 0.17 µm is used.
TABLE 1 Typical Gas Chromatographic ConditionsA 7.2 The column used should be capable of sustaining
Initial Oven Temperature −20 °C temperatures of 435 °C under temperature programming. Alu-
Initial Oven Time 0 min minum covered fused silica and metal columns have been
Oven Temperature Program 15 °C ⁄ min
Final Oven Temperature 425 °C to 435 °CB
successfully used.
Final Hold Time 10 min 7.3 The column should be capable of eluting carbon number
Inlet Initial TemperatureC
50 °C 100 at its highest temperature. It is important that C100 be
Inlet Temperature Program 15 °C ⁄ min eluted during the temperature program cycle of the oven.
Inlet Final Temperature 425 °C
7.4 Column resolution is determined from the separation of
Column 5 m × 0.53 mm × 0.09B carbons 50 and 52 in the retention time calibration mixture
-0.15 µm PDMS
Column Flow 20 mL/min chromatogram. The resolution should be between 1.8 to 4.0.
Carrier Control Constant Flow See Eq 1 in 13.1.
DetectorD FID 7.5 The column shall be capable of allowing the start of the
Detector Temperature 435 °C elution of n-C5 prior to the solvent elution, which is CS2, at
Detector Gases:
Hydrogen 40 mL/min
−20 °C. The descending edge of the n-C5 peak co-elutes with
Air 450 mL/min the solvent. It is to be noted that at these low temperatures
Make-Up (N2, He) 15 mL/min liquid phases may turn solid, and retention shifts may be
Volume Injected 0.2 µL-0.5 µL-1.0 µLB
observed during the elution of compounds at these low oven
Sample Concentration 2.0 % (m/m) temperatures.
Data Acquisition Rate 10 Hz
Total Acquisition Time 40 min to 50 min 7.6 Column Overloading—The prevention of column over-
A
Conditions used for the interlaboratory study.
loading is carried out by determining the skewness of a
B
Several participants used these conditions. Higher temperatures yield higher selected peak among the components of the retention time
recoveries. calibration mixture chromatogram. Any paraffin with a carbon
C
Use lowest temperature recommended by manufacturer.
D
Use GC manufacturer’s recommendations. number between C12 and C24 may be chosen. The skewness
should be between 0.8 and 2.0. See Eq 2 in 13.2.

3
 D7169 − 16
7.7 Column Flow—Helium is used as carrier. Column flow Other precautionary methods of dissolution are acceptable.
rate is set to 20 mL ⁄min. Careful attention should be given to avoid the ignition of the
CS2 (see 8.1).
8. Reagents and Materials 8.4.4 Transfer a 2 mL aliquot of the final mixture obtained
8.1 Carbon Disulfide (CS2 ), 99+ % pure. (Warning— in 8.4.3 into a 2 mL auto sampler vial and seal it firmly. This
Extremely flammable and toxic liquid.) Used as a solvent to solution can be used for about one week if stored at 4 °C.The
dilute the sample and standards as well. Use gloves and safety contents of this vial are injected in order to obtain the retention
glasses when handling the CS2 in a well-ventilated area or time–boiling point curve.
fume hood. It is recommended to use adjustable-volume bottle NOTE 1—Polywax is a trademark of the Baker Petrolite Corporation
dispensers and/or pipettors to minimize direct handling and (Barnsdall, OK). This retention time calibration mixture is commercially
avoid cross-contamination of CS2. Wash vials containing CS2 available from chromatographic supply houses as well as from companies
should be capped with a solvent resistant septa. that build simulated distillation analyzers. The retention time calibration
mixture may differ among supply houses in that docosane, tetracosane and
8.2 Polywax 655 or Polywax 1000—Used as a component hexacosane are also added to the Polywax 655 or Polywax 1000 in order
of the retention time calibration mixture. Since these Poly- to enhance the concentration of these hydrocarbons in the polywaxes.
waxes have carbon 22 as the first component, it shall be 8.5 Detector Relative Response Test Mixture—It is neces-
complemented with the mixture of paraffins described in 8.4.1 sary to initially validate the response of the entire gas chro-
and 8.4.3 so that the entire range of carbon numbers (C5-C100) matographic system. Since this test method assumes that all
is present in the sample. hydrocarbons have the same relative response regardless of
8.3 Paraffıns—The following normal paraffins are used in their retention time, a solution shall be prepared in order to
the preparation of the retention time calibration mixture: determine the relative response factors. An alternative proce-
dure is to use a gravimetric blend as specified in Test Method
pentane undecane heptadecane
hexane dodecane octadecane
D7500.
heptane tridecane nonadecane 8.5.1 Prepare a solution containing the following normal
octane tetradecane eicosane
nonane pentadecane tetracontane
paraffins:
decane hexadecane decane octacosane
tetradecane dotriacontane
8.3.1 The purities of these compounds should be 99 % or octadecane tetracontane
greater. eicosane pentacontane

8.4 Retention Time Calibration Standard—This standard 8.5.2 Weigh about 100 mg of each paraffin to the nearest
can be obtained from chromatography supply companies. This 0.1 mg into a 50 mL volumetric flask. Mix well and add CS2 to
standard is composed of a mixture of Polywax (either P655 or the mark. Ensure that the paraffins are completely dissolved.
P1000) as well as a mixture of paraffins. The addition of the Record the masses of the paraffins, which will be used in Eq 3
paraffin mixture is necessary to cover the range of C5-C20 since in order to calculate the relative response factor of each of the
these paraffins are absent in the Polywax. Furthermore the paraffins.
amounts of the paraffins are chosen so as to facilitate identi- 8.5.3 Record the assayed purity of each paraffin for use in
fying the carbons in the retention time calibration mixture Eq 3.
chromatogram. Alternatively, a successful mixture that has 8.5.4 Transfer an aliquot of the mixture prepared in 8.5.2 to
been used may be prepared by the procedure described in 8.4.1 a 2 mL injection vial. Ensure that the components are in
– 8.4.3 which requires the preparation first of the n -paraffin solution prior to the transfer. Warm the vial if necessary. Inject
mixture (see 8.3) and then spiking an aliquot of this mix to a 0.1 µL to 0.2 µL.
weighed amount of Polywax 655 or 1000.
8.6 Reference Oil 5010—In order to determine the sample
8.4.1 Place approximately 20 mL of CS2 into a round
recovery, the detector response factor has to be determined. For
bottom 50 mL flask. Transfer with care.
this purpose, utilize Reference Oil 5010 as an external stan-
8.4.2 Prepare a mixture of the paraffins listed in 8.3 as dard. This material is obtainable from various chromatography
follows. Weigh 500 mg of each component into a 20 mL vial. suppliers. A gravimetric blend, as described in Test Method
Add an additional 500 mg for dodecane and about 20 mg of D7500, can also be used
tetracontane. Store this mixture at 4 °C and use it as a spiking
mixture in the preparation of the Polywax 655 retention time 8.7 Gases—The following compressed gases are utilized for
calibration mixture. These additional quantities are spiked to the operation of the gas chromatograph:
ease the identification of the n-paraffins; other n-paraffins may 8.7.1 Nitrogen, 99.999 %. (Warning—Compressed gas un-
be chosen as peak markers. der high pressure.) Total impurities should not exceed
8.4.3 Weigh about 25 mg of the Polywax 655 and add it to 10 mL ⁄m3. This gas is used as detector makeup. Helium has
the vessel prepared in 8.4.1. Add approximately 10 mg of the also been used as makeup gas.
paraffin spiking mixture prepared in 8.4.2. Stir the solution 8.7.2 Hydrogen, 99.999 %. (Warning—Extremely flam-
under a fume hood and heat with an infrared lamp (about mable gas under high pressure.) Total impurities should not
200 W) placed at a safe distance (about 15 cm to 20 cm) from exceed 10 mL ⁄m3. This gas is used as fuel for the operation of
the mixture for a period of 20 min or until the solution is clear. the detector.

4
 D7169 − 16
8.7.3 Air, 99.999 %. (Warning—Compressed gas under nearest 0.1 mg. Enter these values in the data acquisition
high pressure and supports combustion.) Total impurities system if appropriate.
should not exceed 10 mL ⁄m3. This gas is used to sustain 10.4 Store all prepared solutions at a temperature of 4 °C.
combustion in the FID detector. Care should be taken that the solution is prepared a short time
8.7.4 Helium, 99.999 %. (Warning—Compressed gas un- prior to running the analysis. Samples can be stored in the auto
der high pressure.) This gas is used as carrier gas and should sampler vials.
not contain more than 5 mL ⁄m3 of O2. The total amount of
impurities should not exceed 10 mL ⁄m3. 10.5 Prepare as many vials of a sample as are necessary to
carry out multiple analyses of that sample. Do not use the same
9. Preparation of the Gas Chromatograph vial to run duplicates; use separate vials containing the same
solution.
9.1 A summary of the conditions used for developing the
precision statement is given in Table 1. 11. Preparation of the Response Factor Standard
9.2 Column Installation—The column is installed using 11.1 Weigh 0.2 g to 0.25 g of Reference Oil 5010 to the
graphite ferrules and an electronic leak detector is used to nearest 0.1 mg. Add 10 mL of CS2 and record the weight of the
ascertain the absence of leaks. Follow the instructions given in solvent to the nearest 0.1 mg. Store this solution at 4 °C, if not
Test Method D2887 and Practice E1510 for the installation of used immediately.
silica or aluminum clad silica columns. Metal columns require
slightly different techniques in cutting and installation. Follow
12. Preparation of the Apparatus and Data System
the recommendations of the column supplier.
12.1 After the column is installed and checked for leaks,
9.3 Detector Temperature—Select a detector temperature
prepare the gas chromatograph to analyze the sample according
that is at least 5 °C to 10 °C higher than the highest oven
to the typical conditions given in Table 1.
temperature.
12.2 Set the acquisition system to digitize the data at 10 Hz.
9.4 Initial Oven Temperature—The initial temperature of
This will result in a slice width of 0.1 s. This data acquisition
the oven is chosen according to the sample type to be analyzed
rate is kept constant for all samples, standards, and the solvent
as follows:
blank in order to acquire the same number of slices. The
9.4.1 Crude Oil Samples—Crude oil samples may contain
baseline chromatogram may contain the same or larger number
hydrocarbons starting from methane, C2, C3, and C4 which
of slices than the sample chromatograms, depending on when
probably co-eleute with C5. Therefore, even at an initial
the data acquisition stops. Thus, various chromatograms taken
temperature of −20 °C, C5 and C6 are partially resolved from
in a sequence may differ by 5 to 10 slices. This fact is of no
the CS2. Further decreases in oven temperature do not increase
consequence with regard to the calculations.
the separation of C5 from C1-C4 hydrocarbons which co-elute
with n-C5. 12.3 Arrange to save the acquired data files. Build the
9.4.2 Residues and Samples Having Higher IBP—For sequence of samples to be injected by the gas chromatograph.
samples that have an initial boiling point of 100°C or greater,
such as vacuum residues or atmospheric residues, the initial 13. Verification of System Performance
oven temperature can be set to between 35 °C and 40 °C. 13.1 Column Resolution—Prepare the gas chromatograph
Ensure that the sample is resolved from the solvent peak at the for injection of the retention time calibration mixture prepared
initial oven temperature selected. If the light ends cannot be in 8.4. Inject 0.1 µL to 0.2 µL of this sample. Determine the
separated from the solvent, then proceed as in 9.4.1. If the user column resolution as follows:
does not know the type of sample to be analyzed, all samples
R 5 2 ~ t 2 2 t 1 ! / ~ 1.699! ~ W 2 1W 1 ! (1)
can be analyzed with an initial temperature of −20 °C.
where:
10. Sample Preparation R = resolution,
10.1 Ensure that the sample is a representative sample. t2 = retention time (s) for the n-C50 paraffin,
Follow the guidelines established in Practice D4057. Samples t1 = retention time (s) for the n-C52 paraffin,
should be handled according to their content of volatile W1 = peak width (s) at half height of the n-C50 peak, and
components. If the sample is submitted for other analyses, W2 = peak width (s) at half height for the n-C52.
remove a small aliquot (~10 mL) early in the testing sequence 13.1.1 Ensure that the resolution, R, is between 1.8 to 4.0.
in order to avoid loss of volatile components. Allow sample to 13.2 Skewness Test for Column Overloading—Select a com-
warm to room temperature prior to weighing. ponent between C12-C24 of the previous chromatogram or of
10.2 Samples that are solid or semi-solid at room tempera- the chromatogram of the retention time calibration mixture
ture may require heating up to as high as 60 °C in order to pour prepared in 8.4. For the component selected, determine the
them into a weighed container. Only samples that are soluble in skewness as follows. The skewness, s, is calculated by Eq 2:
carbon disulfide (CS2) can be analyzed by this test method. ILS participants reported skewness of 0.8 to 2.0 for peaks C7 to
10.3 Weigh 0.2 g to 0.25 g of the sample to the nearest C100.
0.1 mg. Add 10 mL of CS2. Record this weight also to the s 5 ~ a1b ! /2a (2)

5
 D7169 − 16
where: C6, and C7 and shows good peak shape for the C6 and C7
s = skewness of the peak, hydrocarbons. Identify all carbons up to C100.
a = left time segment measured at 10 % of the peak height 14.4 Response Factor Standard—Insert the vial containing
and that intersects the perpendicular from the apex of the Reference Oil 5010 prepared in 8.5, which is used as a
peak to the retention time axis, and response factor standard. Inject this standard in duplicate. A
b = right time segment measured at 10 % of the peak height typical chromatogram of the reference oil analyzed at an initial
and that intersects the perpendicular from the peak apex oven temperature of −20 °C is shown in Fig. A1.3. Verify that
to the retention time axis. Ensure that the skewness is the response factor calculated by Eq 4 does not vary by more
between 0.8 and 2.0. Data acquisition systems can than 2 %.
calculate this parameter.
14.5 Sample Analysis—Insert the sample vials prepared in
13.3 Determination of Detector Relative Response 10.3. Inject samples. Analyzing a QC material with acceptable
Factors—Prepare the gas chromatograph for the injection of results before the analysis of unknown samples is strongly
the detector test mixture prepared in 8.5. Inject 0.1 to 0.2 µL of recommended.
this sample. Calculate the relative response factor, Fi, of each
paraffin relative to eicosane as follows: 14.6 Additional Blank Runs—Insert a vial containing CS2 in
order to obtain a second blank run. Carry out a blank run after
M i 3 P i 3 Ac20
Fi 5 (3) each sample injection, and verify the absence of carryover
A i 3 Mc20 3 Pc20 from the previous samples. An ambient temperature version of
where: the method with faster oven ramping can be employed for these
Mi = mass of the paraffin in mg, clean-out runs in between samples to reduce run time and use
Mc20 = mass of the eicosane in mg, of cryogenic fluids.
Ai = peak area of the paraffin,
Ac20 = peak area of the eicosane, 15. Verification of Acquired Data
Pi = % purity of the paraffin as recorded in 8.5.3, and 15.1 Inspect all chromatograms by loading the data files in
Pc20 = % purity of eicosane.
the data acquisition system. Observe that the signal magnitude
13.3.1 The relative response factor, Fi, should have a value for each sample injected is approximately the same as that for
of between 0.9 and 1.10. Failure to achieve this range may be the retention time calibration mixture and the Reference Oil
due to inlet problems, lack of constant flow, or partial blockage 5010 chromatograms.
of the flame tip orifice, or a combination thereof. 15.2 Verification of the Retention Time Calibration Mixture
Chromatogram—Inspect the chromatograms acquired during a
14. Analytical Sequence sequence run. Do not use a chromatogram where the peaks do
14.1 Set up a sequence of the samples to be analyzed. The not meet the criteria of skewness as defined in 13.2. Inspect the
sequence will contain the order of the samples to be injected chromatogram for the components C5-C7 and the solvent peak
into the column. This schedule should be designed to achieve as shown in the insert of Fig. A1.2. The peaks should not
maximum reproducibility. A suggested order of the samples to present peak splitting nor peak tailing.
be analyzed is described in 14.2 – 14.6. If time constraints 15.3 Sample Chromatograms—Inspect the sample chro-
require a shorter sequence, the user shall ensure that there is no matograms and verify that the chromatograms can be overlaid
carryover between samples and sample types. to a duplicate chromatogram and show that the profile is
14.2 Blank Run—At the beginning of each sequence, after reproducible. Fig. A1.4 shows a chromatogram of a 30°API
any column maintenance is performed, make a blank run. It crude oil where the solvent peak is not resolved from the
may take more than 2 blanks to show a stable plateau with no sample components. Fig. A1.5 shows a typical chromatogram
indication of residual elution. A blank run constitutes an of an atmospheric residue where the solvent peak is resolved
identical solvent injection having the same volume as the from the sample components.
sample injection. An acceptable blank run should show a stable 15.3.1 It is recommended that a QC material be analyzed at
plateau at the highest temperature of the oven (see 15.3). the beginning and end of every sequence. The QC sample
Furthermore, it should not show any indication of carryover or should have the same matrix as the samples analyzed.
residual sample elution. It should also not contain any ghost 15.4 Baseline or Blank Runs—Inspect, in the data system,
peaks. A typical blank sample run is shown in Fig. A1.1. the chromatograms of the blank solvent injections to verify that
Several blanks may be necessary after column installation or the blank signal obtained does not differ substantially from that
after an idle period of the gas chromatograph. Verification of obtained during the sample analysis. Check that the baseline
acceptable blanks is obtained by analyzing the Reference Oil exhibits a gradual rise up to the isothermal section of the
5010 or a gravimetric blend and a QC material. chromatogram and ensure that there is a gradual transition back
14.3 Retention Time Calibration Mixture—Insert the reten- to the plateau of the baseline. Disregard any baseline that
tion time calibration mixture vial prepared in 8.4 into the auto shows material eluting near the highest temperature of the
sampler for injection. A typical chromatogram of the retention column. Also disregard any baseline that shows ghost peaks.
time calibration mixture is shown in Fig. A1.2. The insert in the Overlay the baseline signal with the sample signal as shown in
Fig. A1.2 shows the best separation possible for the C5, CS2, Fig. A1.6. Use only those sample signals that asymptotically

6
 D7169 − 16
approach the baseline signals. Reject any sample run where the of the chromatogram in the data system, that the first 5 slices
baseline signal at the end of the run exceeds in value the contain neither sample nor solvent elution.
sample run. Reject any sample run at which at the end of the 16.1.2 Set up an array that contains slices obtained from the
run the signal exceeds the baseline signal by 10 %. It is Reference Oil 5010 chromatogram. Calculate the average of
recommended that a new full blank analysis be performed at the first five area slices. Subtract the average slice area from
regular intervals (for example, after every 4 to 5 samples) in a each slice in the Reference Oil 5010 chromatogram. Set
sequence of samples to ensure good baseline data for subse- negative numbers to zero.
quent samples. 16.1.3 Zero the blank baseline chromatogram by carrying
15.4.1 Determine the Quenching Interval—Select the time out an analogous calculation as in 16.1.2.
that the solvent peak starts to elute. Determine when the 16.1.4 Blank Baseline Subtraction from the Reference Oil
solvent peak has eluted. Note the times of this interval in 5010 Chromatogram—Subtract each zeroed blank baseline
minutes. An expanded time scale chromatogram of the solvent slice from the corresponding zeroed Reference Oil 5010 slice.
peak is shown in Fig. A1.7. If there are negative slices, set the slice values to zero.
15.4.2 Determine the Magnitude of Solvent Response— 16.1.5 Determination of the End of Elution Time of Refer-
Using the data system, overlay the solvent chromatograms and ence Oil 5010—Since it is a requirement that the sample
verify that the profiles are similar. Verify that the total areas do chosen to obtain a response factor shall fully elute prior to the
not differ by more than 3 % from each other. FEt time, the end of sample elution for this chromatogram is to
15.5 External Standard Response Factor Chromatogram— be determined as described in Test Method D6352, using the
Inspect the external standard chromatogram obtained from the algorithm to determine the time the signal of the completely
injection of Reference Oil 5010. Verify that the boiling point eluted sample returns to baseline.
distribution is within the consensus values as indicated in Test 16.1.6 Determination of the Area of the Chromatogram for
Method D6352. Typical boiling point distribution values for Reference Oil 5010—Determine the end time of solvent elu-
Reference Oil 5010, obtained with this test method, are shown tion. Sum all of the slices from the end of solvent elution to the
in Table 2. Correct any chromatography errors if the consensus end of sample elution. This is the area of the standard, ASTD.
values are not obtained (see 16.1.7). 16.1.7 Calculation of the Boiling Point Distribution of
Reference Oil 5010—The resulting corrected slices obtained
16. Calculations for Reference Oil 5010 are submitted to a Test Method D6352
NOTE 2—The calculations are listed in this section. The chromatogram calculation for boiling point distribution. A comparison of the
for the reference oil, the sample, and the baseline shall be zeroed as given values obtained with the consensus values listed in Table 2
in 16.1.2.
NOTE 3—The baseline chromatogram is subtracted from the Reference shall be made and all the boiling point values shall fall within
Oil 5010 and from the sample chromatogram in order to obtain the net the specified windows. If this requirement is not met, correct
area as shown in 16.1.4. any chromatographic problems prior to proceeding with
16.1 Zeroing of the Reference Oil Chromatogram: sample analysis. Typical problems found in this step are:
16.1.1 Examine the chromatogram obtained for Reference contaminated solvent; problems in sample preparation; sample
Oil 5010 (external standard), and ensure, by visual inspection residue in the inlet or column, or both; quality of the baseline
used, a partially blocked detector jet, or a combination thereof.
16.2 Zeroing of Sample Chromatograms:
TABLE 2 Consensus Values Obtained for the Boiling Point
16.2.1 In the case of crude oil analysis or samples in which
Distribution of Reference Oil 5010 Used as External StandardA the solvent peak is not resolved from the sample components,
%BP avg °C 95.5 %CI, °C avg °F 95.5 %CI, °F ensure, by visual inspection of the chromatogram in the data
IBP 428 9 801 16 system, that the first 5 slices contain neither sample nor solvent
5 477 3 891 5 elution. If there is sample elution, decrease the number of slices
10 493 3 918 5 for the averaging to 3 or increase the digitization rate given in
15 502 3 936 5
20 510 3 950 6 12.2.
25 518 4 963 6 16.2.2 Zeroing the Sample Chromatogram—Proceed in a
30 524 4 975 7
35 531 4 987 7
manner analogous to that described in 16.1.2.
40 537 4 998 8 16.2.3 Zeroing the Blank Baseline Chromatogram—Carry
45 543 4 1008 8 out an analogous calculation as in 16.1.3.
50 548 4 1019 8
55 554 4 1030 8 16.3 Blank Baseline Subtraction from the Sample
60 560 4 1040 8
65 566 4 1051 8
Chromatogram—Carry out an analogous calculation as in
70 572 4 1062 8 16.1.4.
75 578 5 1073 9
80 585 4 1086 8 16.4 Quenching Correction—For crude oil samples, a
85 593 4 1099 7 quenching factor is used to correct for the diminished FID
90 602 4 1116 8
95 616 4 1140 7
response when the CS2 co-elutes with sample components.
FBP 655 18 1213 32 This factor is applied to the time segment corresponding to the
A
As reported in Test Method D6352. elution of CS2. In the interlaboratory study, the factor of 1.930
was applied. This value is determined from experiments made

7
 D7169 − 16
by dissolving butane, pentane, and hexane in toluene. The where:
solution is analyzed by injecting it under conditions identical to ME = mass, in grams, of the sample eluted,
sample analysis. The areas for the components are compared to MSMP = sample mass, in grams, and
the areas obtained by gradually adding weighed aliquots of CS2 MSLSMP = mass of solvent, in grams, used in the sample
to the original solution. Alternatively the quenching value can solution.
be checked by performing a glass distillation by Test Method Since:
D2892. Samples that do not have components that co-elute
with solvent, for example, residues or the Reference Oil 5010, ME 5 ~ A SMP! 3 ~ RF! (6)
do not require the quenching correction. where:
16.4.1 Determine the Quenching Interval—Select the time ASMP = net sample area, and
that the solvent peak starts to elute. Determine when the RF = response factor of the Reference Oil 5010.
solvent peak has eluted. Note the times of this interval in
minutes. An expanded time scale chromatogram of the solvent Substituting Eq 6 for the value of ME in Eq 5 yields:
peak is shown in Fig. A1.7. A SMP 3 RF 3 ~ M SMP1M SLSMP!
%RC 5 3 100 (7)
16.4.2 Locate the slices of the quenching interval. For ~ M SMP!
samples in which the solvent component co-elutes with the Substituting Eq 4 in Eq 7 for the value of RF yields:
sample chromatogram (that is, crude oils), determine the
quenching interval, Q.I., as described in 16.4.1. Find the ~ M STD! ~ M SMP1M SLSMP! A SMP
%RC 5 3 3 3 100 (8)
closest slice corresponding to the beginning of elution of the ~ M STD1M SLSTD! M SMP A STD
solvent peak as well as the final slice corresponding to the end 16.8.1 Determine whether the %recovery, (%RC) falls be-
of elution of the solvent peak. low the recovery threshold (Rt) limits set. If it is less than or
16.4.3 Correct the diminished response of the interval by equal to the recovery threshold (Rt), use the %recovery (%RC)
multiplying each slice of this interval by the quenching factor, determined in 16.8. If the %recovery is greater than the
Q.F. Use the value as discussed in 16.4. recovery threshold (Rt), then the recovery is set to 100 %. If the
16.5 Determination of the Sample Final Elution Time— %recovery is larger than 102 % (1 standard deviation of the
Determine the time at which the oven reaches the isothermal residue), repeat the analysis or determine the chromatographic
portion of the temperature program. This is usually recognized problem.
as an inflection point in the baseline. This point is called the 16.9 Determination of the Boiling Point Distribution:
final elution time (FEt). The conversion of this slice to 16.9.1 Multiply each slice of the sample chromatogram by
temperature will yield the final elution temperature, FET. This the %recovery as established in 16.8.1. Divide each slice by the
conversion is carried out in 16.9.4. total area of the sample obtained in 16.6. This will express the
16.6 Determination of the Sample Area—The net sample slices in a percent scale.
area is obtained by adding all slices from time t = 0 to the final 16.9.2 Add the slices that will yield 0.5 %, 1 %, 2 %, . . .
elution time, FEt. This net area is the ASMP. %recovery. Determine, at 1 % intervals, the time of the slice
yielding exactly 0.5, 1 %, 2 %, ...%recovery. Use an interpo-
16.7 Calculate the Response Factor, RF, as follows: lation procedure to find the fractional slices required to yield
~ M STD! 1 exactly 0.5, 1 %, ...2 %, ...%recovery.
RF 5 3 (4)
~ M STD1M SLSTD! A STD 16.9.3 Stop the calculation carried out in 16.9.2 when
where: obtaining a slice summation equal to the nearest whole integer
of the %recovery.
RF = response factor,
16.9.4 Convert the retention times to boiling points as
ASTD = net area obtained for the Reference Oil 5010
outlined in the Test Method D6352 algorithm. Use the boiling
chromatogram after baseline subtraction and after
point temperatures listed in Table 3. For each retention time
excluding the solvent peak (this area was deter-
obtained in 16.9.2, find the corresponding temperature from the
mined in 16.1.6),
MSLSTD = solvent mass, in grams, used for Reference Oil Boiling Point vs. Retention Time function as shown in Fig.
dissolution, and A1.8. Calculate the corresponding boiling points as determined
MSTD = mass, in grams, of Reference Oil 5010 used in in the Test Method D2887 algorithm.
preparing the response factor solution. 16.10 Calculation of Cut Point Intervals:
16.7.1 The mass term in Eq 4 has been expressed as a 16.10.1 For the two temperatures that define the cut point
fraction of the mass of solute and solvent. interval, find the two corresponding slices.
16.10.2 Using the calibration curve, convert this tempera-
16.8 Calculation of the %Recovery—The %recovery is ture range to a time range.
defined as: 16.10.3 Convert the time range to a slice number range by
~ ME! ME 3 ~ M SMP1M SLSMP! multiplying by 60 and dividing by the slice width in seconds.
%RC 5 3 100 5 3 100
S M SMP
~ M SMP1M SLSMP! D M SMP 16.10.4 Sum the normalized slices, starting with the initial
slice of the cut and terminating with the last slice after the cut.
(5) This sum will be equal to the %mass of the cut.

8
 D7169 − 16
TABLE 3 Boiling Points Of ParaffinsA
Carbon Boiling Boiling Carbon Boiling Boiling
Number Point °C Point °F Number Point °C Point °F
1 –162 –259 51 579 1074
2 –89 –129 52 584 1083
3 –42 –44 53 588 1090
4 0 31 54 592 1098
5 36 97 55 596 1105
6 69 156 56 600 1112
7 98 209 57 604 1119
8 126 258 58 608 1126
9 151 303 59 612 1134
10 174 345 60 615 1139
11 196 385 61 619 1146
12 216 421 62 622 1152
13 235 456 63 625 1157
14 254 488 64 629 1164
15 271 519 65 632 1170
16 287 548 66 635 1175
17 302 576 67 638 1180
18 316 601 68 641 1186
19 330 626 69 644 1191
20 344 651 70 647 1197
21 356 674 71 650 1202
22 369 695 72 653 1207
23 380 716 73 655 1211
24 391 736 74 658 1216
25 402 755 75 661 1222
26 412 774 76 664 1227
27 422 791 77 667 1233
28 431 808 78 670 1238
29 440 825 79 673 1243
30 449 840 80 675 1247
31 458 856 81 678 1252
32 466 870 82 681 1258
33 474 885 83 683 1261
34 481 898 84 686 1267
35 489 912 85 688 1270
36 496 925 86 691 1276
37 503 937 87 693 1279
38 509 948 88 695 1283
39 516 961 89 697 1287
40 522 972 90 700 1292
41 528 982 91 702 1296
42 534 993 92 704 1299
43 540 1004 93 706 1303
44 545 1013 94 708 1306
45 550 1022 95 710 1310
46 556 1033 96 712 1314
47 561 1042 97 714 1317
48 566 1051 98 716 1321
49 570 1058 99 718 1324
50 575 1067 100 720 1328
A
Boiling Points from C1-C92 are taken from Test Method D6352.For carbons C92-C100 taken from reference in Annex 1 of Test Method D6352.

NOTE 1—API Project 44, October 31, 1972 is believed to have provided the original normal paraffin boiling point data that are listed in Table 3.
However, over the years some of the data contained in both API Project 44 (Thermodynamics Research Center Hydrocarbon Project) and Test Method
D6352 have changed and they are no longer equivalent. Table 3 represents the current normal paraffin boiling point values accepted by Subcommittee
D02.04 and found in all test methods under the jurisdiction of Section D02.04.0H.
NOTE 2—Test Method D6352 has traditionally used n-paraffin boiling points rounded to the nearest whole degree for calibration. The boiling points
listed in Table 3 are correct to the nearest whole number in both degrees Celsius and degrees Fahrenheit. However, if a conversion is made from one
unit to the other and then rounded to a whole number, the results will not agree with the table values for a few carbon numbers. For example, the boiling
point of n-heptane is 98.425 °C, which is correctly rounded to 98 °C in the table. However, converting 98.425 °C gives 209.165 °F, which rounds to
209 °F, while converting 98 °C gives 208.4 °F, which rounds to 208 °F. Carbon numbers 2, 4, 7, 8, 9, 13, 14, 15, 16, 25, 27, and 32 are affected by
rounding.

16.10.5 The %recovery, RC, determined at a temperature where:

TRC that is equal to or less than FET, can be determined at a ERC = estimated recovery at temperature T,
new temperature TN by using the following equation: %RC = %recovery determined at temperature TRC in
~ RC 2 R C21% ! 16.8.1,
~ T RC 2 T RC21% ! ~
E RC 5 3 T 2 T RC21% ! 1R C21% (9)

9
 D7169 − 16

%RC-1% = %recovery determined at 1 % below the %RC, 18.1.1 Repeatability—The difference between successive
and test results obtained by the same operator with the same
TRC-1% = temperature corresponding to RC-1%. apparatus under constant operating conditions on identical test
Material would, in the long run, in the normal and correct
16.10.5.1 The use of this equation for values TN > FET is
Operation of the test method, exceed the values in only one
not recommended.
case in twenty as shown in Table 4 (Residues), Table 5 (Crude
17. Report Oil), and Table 6 for Cuts (as used in the ASTM Crosscheck for
Crude Oils).
17.1 Report the temperatures to the nearest 0.5 °C (1 °F) at
18.1.2 Reproducibility—The difference between two single
1 % intervals between 1 % and up to the nearest integer of the
and independent test results obtained by different operators
lower boundary of the %RC. Report also the initial boiling
working in different laboratories on identical test material
point (IBP). Report the selected cut point intervals.
would, in the long run, in the normal and correct operation of
18. Precision and Bias3 the test method, exceed the values shown in Table 4
(Residues), Table 5 (Crude Oil), and Table 6 for Cuts (as used
18.1 Precision—The precision of this test method was in the ASTM Crosscheck for Crude Oils).
determined by the statistical examination of the interlaboratory
test results for five crude oils and five residues. It is important 18.2 Bias—The bias in results of this test method cannot be
to note that the Results for the precision statement as shown in determined because the boiling range distribution is defined by
Tables 4-6 are to be used only within the ranges shown in the the test method.
tables. Additional studies are required to expand the precision
to the ranges not listed in Tables 4-6, respectively. 19. Keywords
19.1 boiling point distribution; crude oils; cut point inter-
3
Supporting data have been filed at ASTM International Headquarters and may vals; distillation residues; lubricants; residues; simulated
be obtained by requesting Research Report RR:D02-1724. distillation

TABLE 4 Repeatability and Reproducibility for ResiduesA

Repeatability, r Reproducibility, R Range Covered
% (mass/mass) °C °F °C °F °C °F
recovered
IBP 5.72 10.3 13.7 24.7 246 to 504 474 to 939
5 3.39 6.1 5.75 10.4 315 to 547 599 to 1017
10 3.19 5.7 5.39 9.7 346 to 563 654 to 1045
15 2.88 5.2 5.2 9.4 368 to 575 694 to 1067
20 3.42 6.2 6.5 11.7 388 to 585 730 to 1085
25 3.55 6.4 6.71 12.1 405 to 595 761 to 1103
30 3.93 7.1 7.6 13.7 420 to 604 788 to 1119
35 4.38 7.9 8.9 16.0 434 to 614 813 to 1137
40 5.22 9.4 11 19.8 447 to 624 836 to 1155
45 6.27 11.3 13.5 24.3 462 to 634 863 to 1173
50 7.18 12.9 16.4 29.5 477 to 645 890 to 1193
55 8.64 15.6 19.9 35.8 493 to 656 919 to 1213
60 10.1 18.2 22.6 40.7 509 to 670 948 to 1238
65 11.7 21.1 24.7 44.5 529 to 684 984 to 1263
70 15.2 27.4 27.4 49.3 550 to 699 1022 to 1290
75 16.6 29.9 30.9 55.6 574 to 716 1065 to 1321
A
Do not extrapolate outside of the above reported data.

10
 D7169 − 16
TABLE 5 Repeatability and Reproducibility for Crude OilA
Repeatability, r Reproducibility, R Range Covered
% (mass/mass) °C °F °C °F °C °F
recovered
IBP 1.35 2.4 2.49 4.5 30 to 31 86 to 88
5 8.94 16.1 19.6 35.3 76 to 97 169 to 207
10 11.4 20.5 19.5 35.1 109 to 154 228 to 309
15 8.23 14.8 15.1 27.2 134 to 217 273 to 423
20 7.51 13.5 13.1 23.6 160 to 259 320 to 498
25 8.7 15.7 13.6 24.5 184 to 295 363 to 563
30 8.22 14.8 13.1 23.6 210 to 327 410 to 621
35 8.52 15.3 14 25.2 231 to 358 448 to 676
40 8.83 15.9 14.9 26.8 249 to 398 480 to 748
45 8.99 16.2 15.1 27.2 265 to 436 509 to 817
50 9.88 17.8 16.4 29.5 285 to 325 545 to 887
55 10.8 19.4 18.6 33.5 304 to 517 579 to 963
60 12.4 22.3 21.5 38.7 326 to 563 619 to 1045
65 13.8 24.8 24.3 43.7 351 to 608 664 to 1126
70 14.3 25.7 21.2 38.2 379 to 608 714 to 1126
75 15.1 27.2 28.24 50.8 410 to 700 770 to 1292
A
Do not extrapolate outside of the above reported data.

TABLE 6 Repeatability and Reproducibility for Cut PointsA

Cut from Set Cut Temperature, Cut Temperature, Repeatability, r Reproducubility, R
to Temperature °C °F Mass % Mass %
Crude Cut 1 82.2 180 1.24 1.74
Crude Cut 2 193.3 380 1.42 1.92
Crude Cut 3 248.9 480 1.48 2.05
Crude Cut 4 343.3 650 1.63 2.28
Crude Cut 5 426.7 800 1.78 2.58
Crude Cut 6 565.6 1050 2.1 3.03
Crude Cut 7 596.1 1105 2.03 3.12
Crude Cut 8 720 1328 2.52 3.17
Residue Cut 1 330 626 0.0748 X 0.126 X
Residue Cut 2 450 842 0.0767 X 0.109 X
Residue Cut 3 600 1112 0.0338 (X + 30) 0.0726 (X + 30)
Residue Cut 4 720 1328 5.36 7.16
A
X= % mass recovered at the cut. Do not extrapolate outside of the above reported data.

ANNEX

(Mandatory Information)

A1. CHROMATOGRAMS AND FIGURES

11
 D7169 − 16

FIG. A1.1 Typical Blank Run (Initial Temperature −20 °C)

FIG. A1.2 Chromatogram of the Retention Time Calibration Mixture C5-C100 Injected at −20 °C,
Insert Expands View of C5-C7 Region

12
 D7169 − 16

FIG. A1.3 Chromatogram (Baseline Corrected) of Reference Oil 5010 Injected at −20 °C

FIG. A1.4 Chromatogram (Baseline Corrected) of a Crude Oil (Injected at −20 °C)

13
 D7169 − 16

FIG. A1.5 Chromatogram (Baseline Corrected) of an Atmospheric Residue

14
 D7169 − 16

FIG. A1.6 Correct and Incorrect Relative Position of Baseline and Sample Signal

FIG. A1.7 Expanded Chromatogram of a CS2 Injection for Selecting the Quenching Interval

15
 D7169 − 16

FIG. A1.8 Boiling Point versus Retention Time Plot

APPENDIX

(Nonmandatory Information)

X1. LIGHT END ANALYSIS FOR CRUDE OILS BY DETAILED HYDROCARBON ANALYSIS

X1.1 Summary X1.1.4 The distillation curve from the first step can then be
combined with the distillation curve in the second step using a
X1.1.1 For samples that contain large amounts of light specific software.
components in the range of C1-C9, and for samples that require
a more accurate description of the boiling curve in the region X1.2 Apparatus and Procedure
C1-C9, it may be necessary to carry out a light end analysis. X1.2.1 A typical schematic of the instrument using a valve
The analysis is carried out in two steps. (8 port staggered or 10 port axial) is shown in the Fig. X1.1.
X1.1.1.1 The first step is to analyze the sample in a separate Alternatively, the same procedure can be achieved using Deans
gas chromatograph which contains an inlet, a pre-fractionator, switch. Additional configurations can be found in Test Method
a column such as is used in Test Method D7900, and a flame D7900. All of the configurations described in Test Method
ionization detector. D7900 have the purpose of allowing the C1-C9 components to
elute into the capillary column and backflush the remaining
X1.1.1.2 The second step is to analyze the sample by a High matrix.
Temperature Gas Chromatograph as described in Sections 1 –
X1.2.2 Details of the sample preparation as well as the use
16 of this test method.
of an internal standard are detailed in Test Method D7900.
X1.1.2 From the first step a detailed composition is obtained
X1.3 Combined Distillation Curve
for the fraction C1-C9 in the crude oil sample. Since the
composition is known and the boiling points of the components X1.3.1 Fig. X1.2 shows the combination of the two curves
are also known, a distillation curve can be obtained. obtained from the two separate instrument analyses. The curve
obtained from the pre-fractionator detailed hydrocarbon analy-
X1.1.3 From the second step a distillation curve is deter- sis is joined with the high temperature simulated distillation
mined as described in Sections 1 – 16 of this test method. curve at the point of intersection as shown in Fig. X1.2.

16
 D7169 − 16

FIG. X1.1 Schematic Diagram of the Prefractionating System

17
 D7169 − 16

FIG. X1.2 Corrected and Uncorrected Distillation Curves

SUMMARY OF CHANGES

Subcommittee D02.04 has identified the location of selected changes to this standard since the last issue
(D7169 – 11) that may impact the use of this standard. (Approved Oct. 15, 2016.)

(1) Added Test Methods D7500 and D7900 to Referenced (6) Added cautionary statements to the use of carbon disulfide.
Documents; added citations throughout. (7) Added verification of blank acceptance.
(2) Eliminated the references to Test Methods D6729 and (8) Added a recommendation to analyze a QC when analyzing
D6730. samples.
(3) Added in Section 4 the use of a gravimetric blend as an (9) Removed requirements to store samples at sub ambient
alternative to measure detector response. temperatures.
(4) Expanded GC variables to be typical. (10) Added the frequency of baselines and cleaning runs.
(5) Increased skewness range to 2. (11) Corrected two typographical boiling point errors.

18
 D7169 − 16
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19