This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles

for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

Designation: D7169 − 19

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, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use.
1.3 This test method is used for the determination of boiling
Specific warning statements are given in Section 8.
point distribution of crude oils. This test method uses capillary
1.8 This international standard was developed in accor-
columns with thin films, which results in the incomplete
dance with internationally recognized principles on standard-
separation of C4-C8 in the presence of large amounts of carbon
disulfide, and thus yields an unreliable boiling point distribu- ization established in the Decision on Principles for the
tion corresponding to this elution interval. In addition, quench- Development of International Standards, Guides and Recom-
ing of the response of the detector employed to hydrocarbons mendations issued by the World Trade Organization Technical
eluting during carbon disulfide elution, results in unreliable Barriers to Trade (TBT) Committee.
quantitative analysis of the boiling distribution in the C4-C8
2. Referenced Documents
region. Since the detector does not quantitatively measure the
carbon disulfide, its subtraction from the sample using a 2.1 ASTM Standards:2
solvent-only injection and corrections to this region via D2887 Test Method for Boiling Range Distribution of Pe-
quenching factors, results in an approximate determination of troleum Fractions by Gas Chromatography
the net chromatographic area. A separate, higher resolution gas D2892 Test Method for Distillation of Crude Petroleum
chromatograph (GC) analysis of the light end portion of the (15-Theoretical Plate Column)
sample may be necessary in order to obtain a more accurate D4057 Practice for Manual Sampling of Petroleum and
description of the boiling point curve in the interval in question Petroleum Products
as described in Test Method D7900 (see Appendix X1). D6352 Test Method for Boiling Range Distribution of Pe-
troleum Distillates in Boiling Range from 174 °C to
1.4 This test method is also designed to obtain the boiling
700 °C by Gas Chromatography
point distribution of other incompletely eluting samples such as
D7500 Test Method for Determination of Boiling Range
atmospheric residues, vacuum residues, etc., that are charac-
Distribution of Distillates and Lubricating Base Oils—in
terized by the fact that the sample components are resolved
Boiling Range from 100 °C to 735 °C by Gas Chroma-
from the solvent.
tography
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 Dec. 1, 2019. Published December 2019. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 2005. Last previous edition approved in 2018 as D7169 – 18. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D7169-19. the ASTM website.

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

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 D7169 − 19
D7900 Test Method for Determination of Light Hydrocar- 3.1.12.1 Discussion—Normally 0.1 s is used. In cases where
bons in Stabilized Crude Oils by Gas Chromatography sample elutes immediately after injection, 0.05 s is used.
E594 Practice for Testing Flame Ionization Detectors Used 3.1.13 start elution temperature (SET), n—the temperature
in Gas or Supercritical Fluid Chromatography at which the first amount of hydrocarbon is detected by the
E1510 Practice for Installing Fused Silica Open Tubular flame ionization detector above a predetermined threshold.
Capillary Columns in Gas Chromatographs
3.1.14 %recovery (RC), n—percentage of the sample eluted.
3. Terminology 3.1.14.1 Discussion—%Recovery is calculated from the
sample area (ASMP), the response factor (RF), the sample mass,
3.1 Definitions of Terms Specific to This Standard:
(MSMP), and the solvent mass (MSLSMP) used in sample
3.1.1 cut point interval, n—the mass % obtained between
dissolution.
two selected temperatures of the interval.
3.1.15 %recovery threshold (Rt) , n—if the %recovery falls
3.1.2 data acquisition rate, n—the speed of conversion of
above a preset limit, the sample is considered fully eluted and
the analog signal to a digital signal, expressed in Hz (cycles/
its recovery is assumed to be 100 %.
second).
3.1.15.1 Discussion—If the %recovery values found for
3.1.3 final boiling point (FBP), n—the temperature, for fully duplicate analyses of a nearly completely eluting sample are
eluting samples (recovery = 100 %), at which 99.5 % of the 99.6 % and 101.2 %, the %recovery threshold (Rt) may be set
sample is eluted. 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 fully eluted and set to 100 %.
component of the reference time standard sample that elutes at 3.2 Symbols:
the end of the temperature ramp of the oven. 3.2.1 ASMP—net area of the sample
3.1.5 final elution temperature (FET), n—the boiling point 3.2.2 ASTD—net area of the response factor standard
of the normal paraffin that elutes at the time when the oven
reaches its final temperature. 3.2.3 MSL—mass of solvent used in preparing sample solu-
tion
3.1.6 initial boiling point (IBP), n—the temperature corre-
sponding to an accumulated 0.5 % of the total area of the eluted 3.2.4 MSLSTD—mass of solvent used in preparing the re-
sample after correcting for the percent of sample recovery. sponse factor standard solution
3.1.7 quenching factor (QF), n—a number that corrects for 3.2.5 MSMP—sample mass used in sample preparation
the diminished response due to the solvent profile co-eluting 3.2.6 MSTD—mass of the standard used in preparing the
with sample components. response factor solution
3.1.7.1 Discussion—Data acquired during the quenching
interval (QI) shall be corrected by applying the quenching 4. Summary of Test Method
factor. 4.1 This is a gas chromatographic method utilizing an inlet
3.1.8 quenching interval (QI), n—the time interval of the and a capillary column, both of which are subject to a
start and end of elution of the CS2 used as a solvent. temperature program. A flame ionization detector is used as a
3.1.8.1 Discussion—Sample components that elute during transducer that converts mass to an electrical signal A data
this time interval shall be corrected by a factor due to their acquisition system operating in the slice mode and chromatog-
diminished response resulting from the co-elution of the raphy software is used to accumulate the electronic signal. A
relatively large amount of solvent present in the sample with retention time calibration mixture is used to develop a retention
the light sample components. time versus boiling point curve. A solution of the Reference Oil
5010 or a gravimetric blend, which fully elutes from the
3.1.9 residue (R), n—the mass % of the sample that has not
column under the conditions of the test method and whose
eluted at the temperature of calculation.
boiling point distribution have been characterized in Test
3.1.9.1 Discussion—Residue is calculated from the %recov-
Method D6352 or D7500, is used to determine the detector
ery.
response factor. Solvent injections are made, and the resulting
3.1.10 response factor (RF), n—the factor used in order to signal is subtracted from both the response factor standard and
calculate the %recovery of the sample. the sample chromatogram. Finally, the sample solution is
3.1.10.1 Discussion—The response factor is determined injected and with the use of the response factor, the amount of
from the net area of the standard (ASTD), mass of standard sample recovered is calculated. After converting the retention
(MSTD), and mass of solvent (MSLSTD) used in the solution of times of the sample slices to temperature, the boiling point
the standard. A fully eluting sample, such as Reference Oil distribution can be calculated up to the recovered amount.
5010, is used in obtaining the response factor.
3.1.11 sample area obtained (ASMP) , n—the net chromato- 5. Significance and Use
graphic area (after baseline subtraction) obtained for the 5.1 The determination of the boiling point distribution of
sample at the final elution time or temperature. crude oils and vacuum residues, as well as other petroleum
3.1.12 slice, n—the reciprocal of the data acquisition rate; fractions, yields important information for refinery operation.
the time interval used to accumulate data, expressed in sec- These boiling point distributions provide information as to the
onds. potential mass percent yield of products. This test method may

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 D7169 − 19
provide useful information that can aid in establishing opera- 6.2 Carrier Gas Purification System—Gas purifiers are used
tional conditions in the refinery. Knowledge of the amount of in order to remove traces of oxygen as well as moisture and
residue produced is important in determining the economics of other impurities present in the carrier gas. The purification
the refining process. system should contain a hydrocarbon trap and an oxygen trap.
The latter should preferably have a visible indicator in order to
6. Apparatus assess the remaining capacity of the oxygen trap.
6.1 Gas Chromatograph—A gas chromatograph provided 6.3 Data System—A data system composed of a computer
with a cryogenic valve for cooling the oven to sub ambient and software for data acquisition, which digitizes the detector
temperatures is required. Typical conditions of operating the signal, is recommended. Some instrumentation digitizes the
Gas Chromatograph are given in Table 1. It shall also have the signal at the electrometer board in order to reduce noise. The
following components: data system is used at acquisition rates of about 10 Hz, which
6.1.1 Flame Ionization Detector (FID)—A flame ionization correspond to slices of 0.1 s. This rate of data acquisition is
detector capable of maintaining a temperature 5 °C to 10 °C necessary to obtain a minimum number of slices void of
higher than the highest column temperature. The flame ioniza- sample or solvent elution immediately after injection. Data
tion detector should possess a jet orifice of about 0.018 in. acquisition systems facilitate the inspection of the baseline
(0.45 mm) in order to delay the plugging of the orifice due to under high magnification and allow the inspection of the
column bleed. The FID should possess a sensitivity of retention time calibration mixture chromatogram. Retention
0.005 coulombs ⁄g (see Practice E594) and should have a linear time shifts can be measured. Overlaying chromatograms is also
range of 106. possible to ascertain similar signal amplitude.
6.1.2 Inlet—Either a temperature programmable inlet with a
6.4 Automatic Sample Injector—It is mandatory to use an
glass liner or a cool-on-column inlet can be used. The inlet
auto sampler since the external standard technique used in this
shall be capable of operating in a temperature-programmed
analysis requires identical volumes for all injections.
mode from 50 °C to the final temperature of the oven. It is
Additionally, small volumes (0.1 µL to 0.2 µL) shall be injected
important that the temperature of the inlet, at any time during
in a reproducible manner. Syringes of 5 µL to 10 µL having
the analysis, be either equal to or greater than the oven
needle gauges of size 23 to 26 are to be used.
temperature. With the use of either inlet, frequent replacement
of the liner or removal of a section of the column may be 6.5 Carrier Gas Control—The gas chromatograph shall be
required due to accumulation of non-volatile sample compo- operated under constant flow conditions. The flow rate at the
nents. It is important that a leak free seal be reestablished after beginning of the oven temperature program shall not differ by
replacement of the liner or the removal of a small section of the more than 1 % from the flow measured at the final oven
column. temperature. Electronic pneumatic control is highly recom-
mended.
7. Column and Column Performance Criteria
TABLE 1 Typical Gas Chromatographic ConditionsA
Initial Oven Temperature −20 °C
7.1 A 100 % bonded polydimethylsiloxane column having a
Initial Oven Time 0 min nominal inside diameter of 0.5 mm and a film thickness of
Oven Temperature Program 15 °C ⁄ min 0.09 µm to 0.17 µm is used.
Final Oven Temperature 425 °C to 435 °CB
Final Hold Time 10 min 7.2 The column used should be capable of sustaining
temperatures of 435 °C under temperature programming. Alu-
Inlet Initial TemperatureC 50 °C
Inlet Temperature Program 15 °C ⁄ min minum covered fused silica and metal columns have been
Inlet Final Temperature 425 °C successfully used.
Column 5 m × 0.53 mm × 0.09B 7.3 The column should be capable of eluting carbon number
-0.15 µm PDMS 100 at its highest temperature. It is important that C100 be
Column Flow 20 mL/min
Carrier Control Constant Flow eluted during the temperature program cycle of the oven.
7.4 Column resolution is determined from the separation of
DetectorD FID
Detector Temperature 435 °C carbons 50 and 52 in the retention time calibration mixture
Detector Gases: chromatogram. The resolution should be between 1.8 to 4.0.
Hydrogen 40 mL/min
Air 450 mL/min
See Eq 1 in 13.1.
Make-Up (N2, He) 15 mL/min 7.5 The column shall be capable of allowing the start of the
Volume Injected 0.2 µL-0.5 µL-1.0 µLB
elution of n-C5 prior to the solvent elution, which is CS2, at
Sample Concentration 2.0 % (m/m) −20 °C. The descending edge of the n-C5 peak co-elutes with
Data Acquisition Rate 10 Hz the solvent. It is to be noted that at these low temperatures
Total Acquisition Time 40 min to 50 min
A
liquid phases may turn solid, and retention shifts may be
Conditions used for the interlaboratory study.
B
Several participants used these conditions. Higher temperatures yield higher
observed during the elution of compounds at these low oven
recoveries. temperatures.
C
Use lowest temperature recommended by manufacturer.
D
Use GC manufacturer’s recommendations. 7.6 Column Overloading—The prevention of column over-
loading is carried out by determining the skewness of a

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 D7169 − 19
selected peak among the components of the retention time under a fume hood and heat with an infrared lamp (about
calibration mixture chromatogram. Any paraffin with a carbon 200 W) placed at a safe distance (about 15 cm to 20 cm) from
number between C12 and C24 may be chosen. The skewness the mixture for a period of 20 min or until the solution is clear.
should be between 0.8 and 2.0. See Eq 2 in 13.2. Other precautionary methods of dissolution are acceptable.
7.7 Column Flow—Helium is used as carrier. Column flow Careful attention should be given to avoid the ignition of the
rate is set to 20 mL ⁄min. CS2 (see 8.1).
8.4.4 Transfer a 2 mL aliquot of the final mixture obtained
8. Reagents and Materials in 8.4.3 into a 2 mL auto sampler vial and seal it firmly. This
8.1 Carbon Disulfide (CS2), 99+ % pure. (Warning— solution can be used for about one week if stored at 4 °C. The
Extremely flammable and toxic liquid.) Used as a solvent to contents of this vial are injected in order to obtain the retention
dilute the sample and standards as well. Use gloves and safety time–boiling point curve.
glasses when handling the CS2 in a well-ventilated area or NOTE 1—Polywax is a trademark of the Baker Petrolite Corporation
fume hood. It is recommended to use adjustable-volume bottle (Barnsdall, OK). This retention time calibration mixture is commercially
dispensers and/or pipettors to minimize direct handling and available from chromatographic supply houses as well as from companies
avoid cross-contamination of CS2. Wash vials containing CS2 that build simulated distillation analyzers. The retention time calibration
should be capped with a solvent resistant septa. mixture may differ among supply houses in that docosane, tetracosane and
hexacosane are also added to the Polywax 655 or Polywax 1000 in order
8.2 Polywax 655 or Polywax 1000—Used as a component to enhance the concentration of these hydrocarbons in the polywaxes.
of the retention time calibration mixture. Since these Poly-
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
their retention time, a solution shall be prepared in order to
8.3 Paraffıns—The following normal paraffins are used in determine the relative response factors. An alternative proce-
the preparation of the retention time calibration mixture: dure is to use a gravimetric blend as specified in Test Method
pentane undecane heptadecane D7500.
hexane dodecane octadecane
heptane tridecane nonadecane 8.5.1 Prepare a solution containing the following normal
octane tetradecane eicosane paraffins:
nonane pentadecane tetracontane
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
weighed amount of Polywax 655 or 1000. 0.1 µL to 0.2 µL.
8.4.1 Place approximately 20 mL of CS2 into a round 8.6 Reference Oil 5010—In order to determine the sample
bottom 50 mL flask. Transfer with care. recovery, the detector response factor has to be determined. For
8.4.2 Prepare a mixture of the paraffins listed in 8.3 as this purpose, utilize Reference Oil 5010 as an external stan-
follows. Weigh 500 mg of each component into a 20 mL vial. dard. This material is obtainable from various chromatography
Add an additional 500 mg for dodecane and about 20 mg of suppliers. A gravimetric blend, as described in Test Method
tetracontane. Store this mixture at 4 °C and use it as a spiking D7500, can also be used
mixture in the preparation of the Polywax 655 retention time
calibration mixture. These additional quantities are spiked to 8.7 Gases—The following compressed gases are utilized for
ease the identification of the n-paraffins; other n-paraffins may the operation of the gas chromatograph:
be chosen as peak markers. 8.7.1 Nitrogen, 99.999 %. (Warning—Compressed gas un-
8.4.3 Weigh about 25 mg of the Polywax 655 and add it to der high pressure.) Total impurities should not exceed
the vessel prepared in 8.4.1. Add approximately 10 mg of the 10 mL ⁄m3. This gas is used as detector makeup. Helium has
paraffin spiking mixture prepared in 8.4.2. Stir the solution also been used as makeup gas.

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 D7169 − 19
8.7.2 Hydrogen, 99.999 %. (Warning—Extremely flam- them into a weighed container. Only samples that are soluble in
mable gas under high pressure.) Total impurities should not carbon disulfide (CS2) can be analyzed by this test method.
exceed 10 mL ⁄m3. This gas is used as fuel for the operation of 10.3 Weigh 0.2 g to 0.25 g of the sample to the nearest
the detector. 0.1 mg. Add 10 mL of CS2. Record this weight also to the
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
combustion in the FID detector. 10.4 Store all prepared solutions at a temperature of 4 °C.
8.7.4 Helium, 99.999 %. (Warning—Compressed gas un- Care should be taken that the solution is prepared a short time
der high pressure.) This gas is used as carrier gas and should prior to running the analysis. Samples can be stored in the auto
not contain more than 5 mL ⁄m3 of O2. The total amount of sampler vials.
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
9.1 A summary of the conditions used for developing the solution.
precision statement is given in Table 1.
11. Preparation of the Response Factor Standard
9.2 Column Installation—The column is installed using
graphite ferrules and an electronic leak detector is used to 11.1 Weigh 0.2 g to 0.25 g of Reference Oil 5010 to the
ascertain the absence of leaks. Follow the instructions given in nearest 0.1 mg. Add 10 mL of CS2 and record the weight of the
Test Method D2887 and Practice E1510 for the installation of solvent to the nearest 0.1 mg. Store this solution at 4 °C, if not
silica or aluminum clad silica columns. Metal columns require used immediately.
slightly different techniques in cutting and installation. Follow
the recommendations of the column supplier. 12. Preparation of the Apparatus and Data System

9.3 Detector Temperature—Select a detector temperature 12.1 After the column is installed and checked for leaks,
that is at least 5 °C to 10 °C higher than the highest oven prepare the gas chromatograph to analyze the sample according
temperature. to the typical conditions given in Table 1.

9.4 Initial Oven Temperature—The initial temperature of 12.2 Set the acquisition system to digitize the data at 10 Hz.
the oven is chosen according to the sample type to be analyzed This will result in a slice width of 0.1 s. This data acquisition
as follows: rate is kept constant for all samples, standards, and the solvent
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
can be analyzed with an initial temperature of −20 °C. R 5 2 ~ t 2 2 t 1 ! / ~ 1.699! ~ W 2 1W 1 ! (1)

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

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 D7169 − 19
skewness as follows. The skewness, s, is calculated by Eq 2: 14.3 Retention Time Calibration Mixture—Insert the reten-
ILS participants reported skewness of 0.8 to 2.0 for peaks C7 to tion time calibration mixture vial prepared in 8.4 into the auto
C100. sampler for injection. A typical chromatogram of the retention
s 5 ~ a1b ! /2a (2) time calibration mixture is shown in Fig. A1.2. The insert in the
Fig. A1.2 shows the best separation possible for the C5, CS2,
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 µL to 0.2 µL recommended.
of 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
reproducible. Fig. A1.4 shows a chromatogram of a 30°API
14.2 Blank Run—At the beginning of each sequence, after
crude oil where the solvent peak is not resolved from the
any column maintenance is performed, make a blank run. It
sample components. Fig. A1.5 shows a typical chromatogram
may take more than 2 blanks to show a stable plateau with no
of an atmospheric residue where the solvent peak is resolved
indication of residual elution. A blank run constitutes an
from the sample components.
identical solvent injection having the same volume as the
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

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 D7169 − 19
to the plateau of the baseline. Disregard any baseline that Oil 5010 and from the sample chromatogram in order to obtain the net
shows material eluting near the highest temperature of the area as shown in 16.1.4.
column. Also disregard any baseline that shows ghost peaks. 16.1 Zeroing of the Reference Oil Chromatogram:
Overlay the baseline signal with the sample signal as shown in 16.1.1 Examine the chromatogram obtained for Reference
Fig. A1.6. Use only those sample signals that asymptotically Oil 5010 (external standard), and ensure, by visual inspection
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.
15.4.1 Determine the Quenching Interval—Select the time 16.1.3 Zero the blank baseline chromatogram by carrying
that the solvent peak starts to elute. Determine when the out an analogous calculation as in 16.1.2.
solvent peak has eluted. Note the times of this interval in 16.1.4 Blank Baseline Subtraction from the Reference Oil
minutes. An expanded time scale chromatogram of the solvent 5010 Chromatogram—Subtract each zeroed blank baseline
peak is shown in Fig. A1.7. slice from the corresponding zeroed Reference Oil 5010 slice.
15.4.2 Determine the Magnitude of Solvent Response— If there are negative slices, set the slice values to zero.
Using the data system, overlay the solvent chromatograms and 16.1.5 Determination of the End of Elution Time of Refer-
verify that the profiles are similar. Verify that the total areas do ence Oil 5010—Since it is a requirement that the sample
not differ by more than 3 % from each other. chosen to obtain a response factor shall fully elute prior to the
15.5 External Standard Response Factor Chromatogram— FEt time, the end of sample elution for this chromatogram is to
Inspect the external standard chromatogram obtained from the be determined as described in Test Method D6352, using the
injection of Reference Oil 5010. Verify that the boiling point algorithm to determine the time the signal of the completely
distribution is within the consensus values as indicated in Test eluted sample returns to baseline.
Method D6352. Typical boiling point distribution values for 16.1.6 Determination of the Area of the Chromatogram for
Reference Oil 5010, obtained with this test method, are shown Reference Oil 5010—Determine the end time of solvent elu-
in Table 2. Correct any chromatography errors if the consensus tion. Sum all of the slices from the end of solvent elution to the
values are not obtained (see 16.1.7). end of sample elution. This is the area of the standard, ASTD.
16.1.7 Calculation of the Boiling Point Distribution of
16. Calculations Reference Oil 5010—The resulting corrected slices obtained
NOTE 2—The calculations are listed in this section. The chromatogram for Reference Oil 5010 are submitted to a Test Method D6352
for the reference oil, the sample, and the baseline shall be zeroed as given
calculation for boiling point distribution. A comparison of the
in 16.1.2.
NOTE 3—The baseline chromatogram is subtracted from the Reference values obtained with the consensus values listed in Table 2
shall be made and all the boiling point values shall fall within
the specified windows. If this requirement is not met, correct
TABLE 2 Consensus Values Obtained for the Boiling Point any chromatographic problems prior to proceeding with
Distribution of Reference Oil 5010 Used as External StandardA sample analysis. Typical problems found in this step are:
%BP avg °C
Allowable
avg °F
Allowable contaminated solvent; problems in sample preparation; sample
Differences, °C Differences, °F residue in the inlet or column, or both; quality of the baseline
IBP 428 9 801 16 used, a partially blocked detector jet, or a combination thereof.
5 477 3 891 5
10 493 3 918 5 16.2 Zeroing of Sample Chromatograms:
15 502 3 936 5
20 510 3 950 6 16.2.1 In the case of crude oil analysis or samples in which
25 518 4 963 6 the solvent peak is not resolved from the sample components,
30 524 4 975 7
35 531 4 987 7
ensure, by visual inspection of the chromatogram in the data
40 537 4 998 8 system, that the first 5 slices contain neither sample nor solvent
45 543 4 1008 8 elution. If there is sample elution, decrease the number of slices
50 548 4 1019 8
55 554 4 1030 8 for the averaging to 3 or increase the digitization rate given in
60 560 4 1040 8 12.2.
65 566 4 1051 8
70 572 4 1062 8
16.2.2 Zeroing the Sample Chromatogram—Proceed in a
75 578 5 1073 9 manner analogous to that described in 16.1.2.
80 585 4 1086 8 16.2.3 Zeroing the Blank Baseline Chromatogram—Carry
85 593 4 1099 7
90 602 4 1116 8 out an analogous calculation as in 16.1.3.
95 616 4 1140 7
FBP 655 18 1213 32 16.3 Blank Baseline Subtraction from the Sample
A
As reported in Test Method D6352. Chromatogram—Carry out an analogous calculation as in
16.1.4.

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16.4 Quenching Correction—For crude oil samples, a 16.8 Calculation of the %Recovery—The %recovery is
quenching factor is used to correct for the diminished FID defined as:
response when the CS2 co-elutes with sample components. ~ ME! ME 3 ~ M SMP1M SLSMP!
This factor is applied to the time segment corresponding to the %RC 5 3 100 5 3 100
elution of CS2. In the interlaboratory study, the factor of 1.930 S M SMP
~ M SMP1M SLSMP! D M SMP

was applied. This value is determined from experiments made (5)

by dissolving butane, pentane, and hexane in toluene. The
solution is analyzed by injecting it under conditions identical to where:
sample analysis. The areas for the components are compared to ME = mass, in grams, of the sample eluted,
the areas obtained by gradually adding weighed aliquots of CS2 MSMP = sample mass, in grams, and
to the original solution. Alternatively the quenching value can MSLSMP = mass of solvent, in grams, used in the sample
be checked by performing a glass distillation by Test Method solution.
D2892. Samples that do not have components that co-elute Since:
with solvent, for example, residues or the Reference Oil 5010,
ME 5 ~ A SMP! 3 ~ RF! (6)
do not require the quenching correction.
16.4.1 Determine the Quenching Interval—Select the time where:
that the solvent peak starts to elute. Determine when the ASMP = net sample area, and
solvent peak has eluted. Note the times of this interval in RF = response factor of the Reference Oil 5010.
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!
16.4.2 Locate the slices of the quenching interval. For %RC 5 3 100 (7)
~ M SMP!
samples in which the solvent component co-elutes with the
sample chromatogram (that is, crude oils), determine the Substituting Eq 4 in Eq 7 for the value of RF yields:
quenching interval, Q.I., as described in 16.4.1. Find the ~ M STD! ~ M SMP1M SLSMP! A SMP
closest slice corresponding to the beginning of elution of the %RC 5 3 3 3 100 (8)
~ M STD1M SLSTD! M SMP A STD
solvent peak as well as the final slice corresponding to the end
of elution of the solvent peak. 16.8.1 Determine whether the %recovery, (%RC) falls be-
16.4.3 Correct the diminished response of the interval by low the recovery threshold (Rt) limits set. If it is less than or
multiplying each slice of this interval by the quenching factor, equal to the recovery threshold (Rt), use the %recovery (%RC)
Q.F. Use the value as discussed in 16.4. determined in 16.8. If the %recovery is greater than the
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
temperature will yield the final elution temperature, FET. This 16.9.1 Multiply each slice of the sample chromatogram by
conversion is carried out in 16.9.4. the %recovery as established in 16.8.1. Divide each slice by the
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
16.7 Calculate the Response Factor, RF, as follows: yielding exactly 0.5, 1 %, 2 %, ...%recovery. Use an interpo-
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
RF = response factor, of the %recovery.
ASTD = net area obtained for the Reference Oil 5010 16.9.4 Convert the retention times to boiling points as
chromatogram after baseline subtraction and after outlined in the Test Method D6352 algorithm. Use the boiling
excluding the solvent peak (this area was deter- point temperatures listed in Table 3. For each retention time
mined in 16.1.6), obtained in 16.9.2, find the corresponding temperature from the
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.

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 D7169 − 19
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.

16.10.2 Using the calibration curve, convert this tempera- 16.10.4 Sum the normalized slices, starting with the initial
ture range to a time range. slice of the cut and terminating with the last slice after the cut.
16.10.3 Convert the time range to a slice number range by This sum will be equal to the %mass of the cut.
multiplying by 60 and dividing by the slice width in seconds.

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16.10.5 The %recovery, RC, determined at a temperature test results for five crude oils and five residues. It is important
TRC that is equal to or less than FET, can be determined at a to note that the Results for the precision statement as shown in
new temperature TN by using the following equation: Tables 4-6 are to be used only within the ranges shown in the
~ RC 2 R C21% ! tables. Additional studies are required to expand the precision
~ T RC 2 T RC21% ! ~
E RC 5 3 T 2 T RC21% ! 1R C21% (9) to the ranges not listed in Tables 4-6, respectively.
18.1.1 Repeatability—The difference between successive
where: test results obtained by the same operator with the same
ERC = estimated recovery at temperature T, apparatus under constant operating conditions on identical test
%RC = %recovery determined at temperature TRC in Material would, in the long run, in the normal and correct
16.8.1, Operation of the test method, exceed the values in only one
%RC-1% = %recovery determined at 1 % below the %RC, case in twenty as shown in Table 4 (Residues), Table 5 (Crude
and Oil), and Table 6 for Cuts (as used in the ASTM Crosscheck for
TRC-1% = temperature corresponding to RC-1%. Crude Oils).
16.10.5.1 The use of this equation for values TN > FET is 18.1.2 Reproducibility—The difference between two single
not recommended. and independent test results obtained by different operators
working in different laboratories on identical test material
17. Report would, in the long run, in the normal and correct operation of
17.1 Report the temperatures to the nearest 0.5 °C (1 °F) at the test method, exceed the values shown in Table 4
1 % intervals between 1 % and up to the nearest integer of the (Residues), Table 5 (Crude Oil), and Table 6 for Cuts (as used
lower boundary of the %RC. Report also the initial boiling in the ASTM Crosscheck for Crude Oils).
point (IBP). Report the selected cut point intervals.
18.2 Bias—The bias in results of this test method cannot be
18. Precision and Bias3 determined because the boiling range distribution is defined by
the test method.
18.1 Precision—The precision of this test method was
determined by the statistical examination of the interlaboratory
19. Keywords
3
Supporting data have been filed at ASTM International Headquarters and may
19.1 boiling point distribution; crude oils; cut point inter-
be obtained by requesting Research Report RR:D02-1724. Contact ASTM Customer vals; distillation residues; lubricants; residues; simulated
Service at service@astm.org. 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.

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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

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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

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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)

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

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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

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FIG. A1.8 Boiling Point versus Retention Time Plot

APPENDIX

(Nonmandatory Information)

X1. ALGORITHM FOR MERGING BOILING POINT DISTRIBUTION RESULTS OF D7900 AND D7169

X1.1 The resulting data from Test Methods D7900 and without such interference. This algorithm generates boiling
D7169 can be used to perform a merge of the D7900 light ends point distribution results that correct this anomaly in the light
boiling point curve with that of D7169, using a variety of end portion of Test Method D7169 by merging the more
mathematical means. accurate results of Test Method D7900.
X1.2 This appendix outlines an algorithm to aid in merging X1.4 Summary of the Procedure
the results of D7900 with those of D7169 to result in a more X1.4.1 The boiling point distribution results from Test
accurate boiling point distribution of the crude oil sample. The Methods D7900 and D7169 for the same sample are collected
algorithm does not attempt to smooth or otherwise alter the in value arrays. They are merged together at a fixed boiling
results of the merged boiling point distribution, relying solely point temperature not to exceed the boiling point of n-nonane
on the original results from Test Methods D7900 and D7169. (the current limit of Test Method D7900 results). A new boiling
Additional mathematical smoothing or fitting is left to the point distribution result is calculated from the merged data.
individual user and his requirements. Recoveries greater than 100 % by mass after the merge are
X1.3 Significance and Use normalized through the D7169-only contribution to the final
results, as the D7900 results are assumed to be accurate as
X1.3.1 The scope of Test Method D7169 includes a caveat reported.
that results for the light end portion of the analysis may be
inaccurate due to the co-elution of the required carbon disulfide
solvent with light hydrocarbons. This results in a diminished or
quenched FID response to those hydrocarbons, resulting in
lower recoveries in this region. Test Method D7900 was
developed to more accurately determine the boiling point
distribution of the front end portion of a crude oil sample

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NOTE X1.1—In a situation such as a heavy crude where there is no TABLE X1.1 Value Array D7900 Cumulative Mass Percent (CMP)
significant amount of light ends at or below C9, then the D7169 data versus BP Degrees Celsius (BP, °C) in 0.01 % by Mass Intervals
should be taken as reported with no merge or light ends correction. Array Row CMP BP (°C)
1 0.50 % –42.04
X1.5 D7900 and D7169 Data Accuracy Determination 2 0.51 % –11.72
3 0.52 % –0.50
X1.5.1 To ensure that the initial D7900 and D7169 data is ... ... ...
comparable in accuracy, determine the cumulative mass per- ... ... ...
cent recovery at the boiling point where the merge is to be C9 21.30 % 150.76

made from each of the D7900 and D7169 results. Calculate the
absolute difference as:
DIFFx 5 ABS~ M 1 2 M 2 ! (X1.1) D7169. For example, a sample containing 5 % by mass n-pentane would
have five successive whole mass percentages occurring at the boiling point
where: of n-pentane (36.06 °C). See Fig. X1.1.
DIFFx = absolute difference in cumulative mass recovery X1.6.1.2 D7169 Mass Percent by BP Data Array, N
between D7900 and D7169 at the merge boiling Elements—Create a two-dimensional value array from the
point, D7169 results (D7169VA) where:
M1 = cumulative mass percent recovered to the merge
D7169VA(i,1) = cumulative percent by mass from D7169 results in percent by
point temperature from D7900, and mass increments no greater than 0.1, and
M2 = cumulative mass percent recovered to the merge
point temperature from D7169. D7169VA(i,2) = boiling point, in °C, at this cumulative percent by mass.

X1.5.2 The absolute difference (DIFFx) in most cases will Begin the array at 0.50 % by mass (defined as initial boiling
not exceed 5.0 % by mass. Values above this may indicate point or IBP) and end the array at the final D7169 cumulative
possible errors in the D7900 or D7169 analyses, or both mass percent recovered. As an example, for a n-nonane merge
(weighing errors, response factor errors, etc.). Further review point using 0.01 % by mass increments, such an array would
of these analytical results and possible re-analysis of the appear as indicated in Table X1.2.
sample may be required.
NOTE X1.4—Anecdotal studies performed by various labs performing
NOTE X1.2—It is possible in very light condensates containing a this merge algorithm found that by using 0.01 % by mass increments for
significant amount of hexanes and lighter that the application of the D7169 the D7900 and D7169 results initially, the need for interpolation is
quench factor could cause marked differences in the two results. In this reduced and the accuracy of the merge point and final result comparability
case, or when the D7900 and D7169 results are determined to be accurate to physical distillation was improved.
within themselves, the D7900 result should be assumed to be the most
accurate, as it is not affected by solvent quenching. X1.7 Data Merging Procedure
X1.6 Elements Required to Perform Merge of D7900 and X1.7.1 The following procedure is used to prepare a result
D7169 at the Merge Point value array (RVA) containing the merged results.
X1.6.1 The following elements must be prepared from the X1.7.1.1 Create a two-dimensional result value array (RVA)
results of Test Methods D7900 and D7169 for the sample. The where:
selected merge point shall not exceed the boiling point of RVA(i,1) = cumulative mass percent in no greater than 0.1 % by mass
increments, and
n-nonane (the boiling point limit of Test Method D7900).
X1.6.1.1 D7900 Mass Percent by BP Value Array, N RVA(i,2) = boiling point, in °C, at that cumulative percent by mass.
Elements—Create a two-dimensional value array from the
D7900 results (D7900VA) where: Initially populate the array with all the elements of the
D7900VA(i,1) = cumulative mass percent from D7900 results in percent by D7900VA (see X1.6.1.1). Store the final row number after all
mass increments of at least 0.1, and D7900 data is added to the RVA, as this may be needed later if
D7900VA(i,2) = boiling point, in °C, at this cumulative percent by mass.
normalization is required (see X1.9).
X1.7.1.2 Search the D7169 cumulative percent by mass
Begin the array at 0.5 % by mass (defined as initial boiling versus BP value array until the row containing the cumulative
point or IBP) and end the array at the cumulative mass percent percent by mass at the merge point is found. Append percent by
recovered at the merge point’s boiling point. As an example, mass values from the D7169 value array to the result value
such an array would appear as indicated in Table X1.1 if array from the first row just after the merge point of the D7169
n-nonane’s boiling point was selected as the merge point and value array as follows:
0.01 % by mass increments are used. For i 5 x to N (X1.2)
NOTE X1.3—There may be elements of the array where multiple RVA~ i , 1 ! 5 RVA~ i 2 1 , 1 ! 1z
cumulative percentages occur at the exact same temperature. This is due RVA~ i , 2 ! 5 D7169VA~ m , 2 !
to the fact that Test Method D7900 is a component-based boiling point
distribution as opposed to the slice-based distribution used in Test Method m 5 m11

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 D7169 − 19

FIG. X1.1 Example of Light End Component Boiling Distribution Showing Multiple Cumulative Percentages at the Boiling Point of Iso-
pentane and Pentane

TABLE X1.2 Value Array D7169 Cumulative Mass Percent (CMP) m = initialized at the array element row num-
versus BP Degrees Celsius (BP, °C) In 0.01 % by Mass Intervals
ber of first D7169VA element just after the
Array Row CMP BP (°C)
1 0.50 % 36.06
merge point from search of array,
2 0.51 % 39.20 RVA(i,1) = result value array cumulative percent by
3 0.52 % 43.55 mass at row i,
... ... ... RVA(i,2) = result value array boiling point (in °C) at
... ... ...
999 23.00 % 150.76 (n-nonane BP) row i,
... ... ... D7169VA(m,1) = D7169 cumulative percent by mass at row
... ... ... m, and
N 94.30 % 712.00
D7169VA(m,2) = D7169 boiling point (in °C) at row m.
X1.8 Reporting Merged Results
Next i X1.8.1 Using the completed result value array (RVA, see
X1.7.1.2), extract the cumulative percent by mass by boiling
where:
point in the desired percent by mass intervals and report.
N = the total number of rows in the D7169VA, Report the initial boiling point (IBP) as the temperature at
x = array element row number for next value which 0.5 % by mass of the sample has eluted, and (if
pair from D7169VA that is just after the applicable) report the final boiling point (FBP) as the tempera-
row at the merge point, ture at which 99.5 % by mass of the sample has eluted. If the
z = increment of mass percentages (for
final RVA recovery is less than or equal to 100.0 % by mass,
example, 0.1, 0.01),
end the report at the last full cumulative percent by mass off.

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 D7169 − 19
The actual final percent by mass recovery and temperature may X1.9.2 Normalize the D7169 mass percentages using the
be reported also, if desired. If the final percent by mass following procedure:
recovery exceeds 100.0 % by mass, follow the procedure in For i 5 x to N (X1.4)
X1.9 to renormalize only the array elements taken from the
D7169 results to give exactly 100.0 % by mass recovery. The RVA~ i , 1 ! 5 RVA~ i 2 1 , 1 ! 1 ~ P 3 D 7169 NF!
D7900 result values should NOT be normalized as these are Next i
assumed to be accurate as reported. Fig. X1.2 demonstrates an
example report. where:
x = array element just after the last D7900 contrib-
NOTE X1.5—For clarity and comparison, it is also suggested to report uted mass percentage,
the original D7169 percent by mass recovery, and the final merged percent
by mass recovery. The difference here again should be less than 5 % by
N = last element of the RVA array,
mass absolute. If higher, see X1.5. P = increment of the cumulative mass percentages
(0.1, 0.01, etc.), and
X1.9 Normalizing Results for Recoveries in Excess of 100 D7169NF = normalization factor to be applied to all D7169
% by Mass After Merging cumulative percent by mass results in the RVA.
X1.9.1 If the chromatographic results for Test Methods X1.9.2.1 The final sum of all cumulative mass percentages
D7900 and D7169 have been verified, and the recovery is in in the RVA (D7900 and D7169 contributed) should now equal
excess of 100.0 % by mass or is greater than a predetermined exactly 100.0 % by mass. Use the normalized RVA to report the
recovery threshold, the following procedure should be used to results (as an example see Fig. X1.2).
normalize the D7169 data only:
~ 100 2 R D7900! NOTE X1.6—Un-normalized percent by mass recovery of the result
D7169NF 5 (X1.3) value array in excess of 105.0 % by mass should be considered suspect.
~ RVA ~ y , 1 ! 2 R D7900! An excess recovery of this magnitude may indicate inaccuracies in the
where: D7900 results, the D7169 results, or both. See X1.5.
D7169NF = normalization factor to be applied to all D7169
cumulative percent by mass results in the RVA,
RD7900 = cumulative percent by mass recovery at the
merge point from D7900, and
y = last row element of the D7169 portion of the
RVA (final percent by mass recovery).

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 D7169 − 19

FIG. X1.2 Example Final Merged Boiling Point Distribution Report

SUMMARY OF CHANGES

Subcommittee D02.04 has identified the location of selected changes to this standard since the last issue
(D7169 – 18) that may impact the use of this standard. (Approved Dec. 1, 2019.)

(1) Revised Table 2.

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 June 1, 2018.)

(1) Replaced former Appendix X1 with new Appendix X1

(Appendix X3 from Test Method D7900).

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