Designation: D6352 − 04 (Reapproved 2009)

Standard Test Method for

Boiling Range Distribution of Petroleum Distillates in
Boiling Range from 174 to 700°C by Gas Chromatography1
This standard is issued under the fixed designation D6352; 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 D2892 Test Method for Distillation of Crude Petroleum

1.1 This test method covers the determination of the boiling (15-Theoretical Plate Column)
range distribution of petroleum distillate fractions. The test D3710 Test Method for Boiling Range Distribution of Gaso-
method is applicable to petroleum distillate fractions having an line and Gasoline Fractions by Gas Chromatography
initial boiling point greater than 174°C (345°F) and a final D4626 Practice for Calculation of Gas Chromatographic
boiling point of less than 700°C (1292°F) (C10 to C90) at Response Factors
atmospheric pressure as measured by this test method. D5307 Test Method for Determination of Boiling Range
Distribution of Crude Petroleum by Gas Chromatography
1.2 The test method is not applicable for the analysis of (Withdrawn 2011)3
petroleum or petroleum products containing low molecular E355 Practice for Gas Chromatography Terms and Relation-
weight components (for example naphthas, reformates, gaso- ships
lines, crude oils). Materials containing heterogeneous compo- E594 Practice for Testing Flame Ionization Detectors Used
nents (for example alcohols, ethers, acids, or esters) or residue in Gas or Supercritical Fluid Chromatography
are not to be analyzed by this test method. See Test Methods E1510 Practice for Installing Fused Silica Open Tubular
D3710, D2887, or D5307 for possible applicability to analysis Capillary Columns in Gas Chromatographs
of these types of materials.
3. Terminology
1.3 The values stated in SI units are to be regarded as
standard. The values stated in inch-pound units are for infor- 3.1 Definitions—This test method makes reference to many
mation only and may be included as parenthetical values. common gas chromatographic procedures, terms, and relation-
1.4 This standard does not purport to address all of the ships. For definitions of these terms used in this test method,
safety concerns, if any, associated with its use. It is the refer to Practices E355, E594, and E1510.
responsibility of the user of this standard to establish appro- 3.2 Definitions of Terms Specific to This Standard:
priate safety and health practices and determine the applica- 3.2.1 area slice—the area resulting from the integration of
bility of regulatory limitations prior to use. the chromatographic detector signal within a specified reten-
tion time interval. In area slice mode (see 6.4.2), peak detection
2. Referenced Documents parameters are bypassed and the detector signal integral is
2.1 ASTM Standards:2 recorded as area slices of consecutive, fixed duration time
D86 Test Method for Distillation of Petroleum Products at intervals.
Atmospheric Pressure 3.2.2 corrected area slice—an area slice corrected for base-
D1160 Test Method for Distillation of Petroleum Products at line offset by subtraction of the exactly corresponding area
Reduced Pressure slice in a previously recorded blank (non-sample) analysis.
D2887 Test Method for Boiling Range Distribution of Pe- 3.2.3 cumulative corrected area—the accumulated sum of
troleum Fractions by Gas Chromatography corrected area slices from the beginning of the analysis through
a given retention time, ignoring any non-sample area (for
1
This test method is under the jurisdiction of ASTM Committee D02 on example, solvent).
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
D02.04.0H on Chromatographic Distribution Methods.
3.2.4 final boiling point (FBP)—the temperature (corre-
Current edition approved April 15, 2009. Published July 2009. Originally sponding to the retention time) at which a cumulative corrected
approved in 1998. Last previous edition approved in 2004 as D6352 – 04´1. DOI: area count equal to 99.5 % of the total sample area under the
10.1520/D6352-04R09. chromatogram is obtained.
2
For referenced ASTM standards, visit the ASTM website, [Link], or
contact ASTM Customer Service at service@[Link]. For Annual Book of ASTM
3
Standards volume information, refer to the standard’s Document Summary page on The last approved version of this historical standard is referenced on
the ASTM website. [Link].

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 D6352 − 04 (2009)
3.2.5 initial boiling point (IBP)—the temperature (corre- method can be used for product specification testing with the
sponding to the retention time) at which a cumulative corrected mutual agreement of interested parties.
area count equal to 0.5 % of the total sample area under the 5.2 This test method extends the scope of boiling range
chromatogram is obtained. determination by gas chromatography to include medium and
3.2.6 slice rate—the time interval used to integrate the heavy petroleum distillate fractions beyond the scope of Test
continuous (analog) chromatographic detector response during Method D2887 (538°C).
an analysis. The slice rate is expressed in Hz (for example 5.3 Boiling range distributions obtained by this test method
integrations or slices per second). have not been analyzed for correlation to those obtained by low
3.2.7 slice time—the analysis time associated with each area efficiency distillation, such as with Test Method D86 or D1160.
slice throughout the chromatographic analysis. The slice time
is the time at the end of each contiguous area slice. 6. Apparatus
3.2.8 total sample area—the cumulative corrected area, 6.1 Chromatograph—The gas chromatographic system used
from the initial area point to the final area point, where the shall have the following performance characteristics:
chromatographic signal has returned to baseline after complete 6.1.1 Carrier Gas Flow Control—The chromatograph shall
sample elution. be equipped with carrier gas pressure or flow control capable of
3.3 Abbreviations—A common abbreviation of hydrocarbon maintaining constant carrier gas flow control through the
compounds is to designate the number of carbon atoms in the column throughout the column temperature program cycle.
compound. A prefix is used to indicate the carbon chain form, 6.1.2 Column Oven—Capable of sustained and linear pro-
while a subscripted suffix denotes the number of carbon atoms grammed temperature operation from near ambient (for ex-
(for example n-C10 for normal-decane, i-C14 for iso- ample, 30 to 35°C) up to 450°C.
tetradecane). 6.1.3 Column Temperature Programmer—The chromato-
graph shall be capable of linear programmed temperature
operation up to 450°C at selectable linear rates up to 20°C/min.
4. Summary of Test Method
The programming rate shall be sufficiently reproducible to
4.1 The boiling range distribution determination by distilla- obtain the retention time repeatability of 0.1 min (6 s) for each
tion is simulated by the use of gas chromatography. A component in the calibration mixture described in 7.5.
non-polar open tubular (capillary) gas chromatographic col- 6.1.4 Detector—This test method requires the use of a flame
umn is used to elute the hydrocarbon components of the sample ionization detector (FID). The detector shall meet or exceed the
in order of increasing boiling point. following specifications in accordance with Practice E594. The
4.2 A sample aliquot is diluted with a viscosity reducing flame jet should have an orifice of approximately 0.05 to 0.070
solvent and introduced into the chromatographic system. mm (0.020 to 0.030 in.).
Sample vaporization is provided by separate heating of the [Link] Operating Temperature—100 to 450°C.
point of injection or in conjunction with column oven heating. [Link] Sensitivity—>0.005 C/g carbon.
[Link] Minimum Detectability—1 × 10-11 g carbon/s.
4.3 The column oven temperature is raised at a specified [Link] Linear Range—>106
linear rate to affect separation of the hydrocarbon components [Link] Connection of the column to the detector shall be
in order of increasing boiling point. The elution of sample such that no temperature below the column temperature exists
components is quantitatively determined using a flame ioniza- between the column and the detector. Refer to Practice E1510
tion detector. The detector signal is recorded as area slices for for proper installation and conditioning of the capillary col-
consecutive retention time intervals during the analysis. umn.
4.4 Retention times of known normal paraffin hydrocarbons, 6.1.5 Sample Inlet System—Any sample inlet system ca-
spanning the scope of the test method, are determined and pable of meeting the performance specification in 7.6 and 8.2.2
correlated to their boiling point temperatures. The normalized may be used. Programmable temperature vaporization (PTV)
cumulative corrected sample areas for each consecutive re- and cool on-column injection systems have been used success-
corded time interval are used to calculate the boiling range fully.
distribution. The boiling point temperature at each reported 6.2 Microsyringe—A microsyringe with a 23-gage or
percent off increment is calculated from the retention time smaller stainless steel needle is used for on-column sample
calibration. introduction. Syringes of 0.1 to 10-µL capacity are available.
6.2.1 Automatic syringe injection is recommended to
5. Significance and Use achieve best precision.
5.1 The boiling range distribution of medium and heavy 6.3 Column—This test method is limited to the use of
petroleum distillate fractions provides an insight into the non-polar wall coated open tubular (WCOT) columns of high
composition of feed stocks and products related to petroleum thermal stability (see Note 1). Glass, fused silica, and stainless
refining processes (for example, hydrocracking, hydrotreating, steel columns with 0.53 to 0.75-mm internal diameter have
visbreaking, or deasphalting). The gas chromatographic simu- been successfully used. Cross-linked or bonded 100 %
lation of this determination can be used to replace conventional dimethyl-polysiloxane stationary phases with film thickness of
distillation methods for control of refining operations. This test 0.10 to 0.20 µm have been used. The column length and liquid

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 D6352 − 04 (2009)
phase film thickness shall allow the elution of at least C90 such specifications are available.4 Other grades may be used,
n-paraffin (BP = 700°C). The column and conditions shall provided it is first ascertained that the solvent is of sufficiently
provide separation of typical petroleum hydrocarbons in order high purity to permit its use without lessening the accuracy of
of increasing boiling point and meet the column performance the determination.
requirements of 8.2.1. The column shall provide a resolution 7.4.1 Carbon Disulfide (CS2)—(99+ % pure) is used as a
between three (3) and ten (10) using the test method operating viscosity-reducing solvent and as a means of reducing mass of
conditions. sample introduced onto the column to ensure linear detector
response and reduced peak skewness. It is miscible with
NOTE 1—Based on recent information that suggests that true boiling asphaltic hydrocarbons and provides a relatively small re-
points (atmospheric equivalent temperatures) versus retention times for all
components do not fall on the same line, other column systems that can
sponse with the FID. The quality (hydrocarbon content) should
meet this criteria will be considered. These criteria will be specified after be determined by this test method prior to use as a sample
a round robin evaluation of the test method is completed. diluent. (Warning—CS2 is extremely flammable and toxic.)
7.4.2 Cyclohexane (C6H12)—(99+ % pure) may be used in
6.4 Data Acquisition System:
place of CS2 for the preparation of the calibration mixture.
6.4.1 Recorder—A 0 to 1 mV range recording potentiometer
or equivalent with a full-scale response time of 2 s or less may 7.5 Calibration Mixture—A qualitative mixture of
be used. It is, however, not a necessity if an integrator/ n-paraffins (nominally C10 to C100) dissolved in a suitable
computer data system is used. solvent. The final concentration should be approximately one
part of n-paraffin mixture to 200 parts of solvent. At least one
6.4.2 Integrator—Means shall be provided for determining
compound in the mixture shall have a boiling point lower than
the accumulated area under the chromatogram. This can be
the initial boiling point and one shall have a boiling point
done by means of an electronic integrator or computer-based
higher than the final boiling point of the sample being
chromatography data system. The integrator/computer system analyzed, as defined in 1.1. The calibration mixture shall
shall have normal chromatographic software for measuring the contain at least eleven known n-paraffins (for example C10,
retention time and areas of eluting peaks (peak detection C12, C16, C20, C30, C40, C50, C60, C70, C80, and C90).
mode). In addition, the system shall be capable of converting Atmospheric equivalent boiling points of n-paraffins are listed
the continuously integrated detector signal into area slices of in Table 1.
fixed duration. These contiguous area slices, collected for the
entire analysis, are stored for later processing. The electronic NOTE 3—A suitable calibration mixture can be obtained by dissolving
a hydrogenated polyethylene wax (for example, Polywax 655 or Polywax
range of the integrator/computer (for example 1 V, 10 V) shall 1000) in a volatile solvent (for example, CS2 or C6H12). Solutions of 1 part
be operated within the linear range of the detector/electrometer Polywax to 200 parts solvent can be prepared. Lower boiling point
system used. paraffins will have to be added to ensure conformance with 7.5. Fig. 1
illustrates a typical calibration mixture chromatogram, and Fig. 2 illus-
NOTE 2—Some gas chromatographs have an algorithm built into their trates an expanded scale of carbon numbers above 75.
operating software that allows a mathematical model of the baseline
profile to be stored in memory. This profile is automatically subtracted 7.6 Response Linearity Mixture—Prepare a quantitatively
from the detector signal on subsequent sample runs to compensate for the weighed mixture of at least ten individual paraffins (>99 %
column bleed. Some integration systems also store and automatically purity), covering the boiling range of the test method. The
subtract a blank analysis from subsequent analytical determinations. highest boiling point component should be at least n-C60. The
mixture shall contain n-C40. Use a suitable solvent to provide
7. Reagents and Materials a solution of each component at approximately 0.5 to 2.0 % by
7.1 Carrier Gas—Helium, hydrogen, or nitrogen of high mass.
purity (Warning —Helium and nitrogen are compressed gases 7.7 Reference Material 5010—A reference sample that has
under high pressure). Additional purification is recommended been analyzed by laboratories participating in the test method
by the use of molecular sieves or other suitable agents to cooperative study. Consensus values for the boiling range
remove water, oxygen, and hydrocarbons. Available pressure distribution of this sample are given in Table 2.
shall be sufficient to ensure a constant carrier gas flow rate.
8. Preparation of Apparatus
7.2 Hydrogen—Hydrogen of high purity (for example, hy-
drocarbon free) is used as fuel for the FID. Hydrogen can also 8.1 Gas Chromatograph Setup:
be used as the carrier gas. ( Warning—Hydrogen is an 8.1.1 Place the gas chromatograph and ancillary equipment
extremely flammable gas under high pressure). into operation in accordance with the manufacturer’s instruc-
tions. Typical operating conditions are shown in Table 3.
7.3 Air—High purity (for example, hydrocarbon free) com-
pressed air is used as the oxidant for the FID. (Warning—
Compressed air is a gas under high pressure and supports
4
combustion). Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
7.4 Solvents—Unless otherwise indicated, it is intended that listed by the American Chemical Society, see Annual Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
all solvents conform to the specifications of the Committee on and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
Analytical Reagents of the American Chemical Society where MD.

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 D6352 − 04 (2009)
TABLE 1 Boiling Points of n-ParaffinsA,B TABLE 1 Continued
Carbon No. Boiling Point, °C Boiling Point, °F Carbon No. Boiling Point, °C Boiling Point, °F
1 –162 –259 76 664 1227
2 –89 –127 77 667 1233
3 –42 –44 78 670 1238
4 0 31 79 673 1243
5 36 97 80 675 1247
6 69 156 81 678 1252
7 98 209 82 681 1258
8 126 258 83 683 1261
9 151 303 84 686 1267
10 174 345 85 688 1270
11 196 385 86 691 1276
12 216 421 87 693 1279
13 235 456 88 695 1283
14 254 488 89 697 1287
15 271 519 90 700 1292
16 287 548 91 702 1296
17 302 576 92 704 1299
18 316 601 93 706 1303
19 330 625 94 708 1306
20 344 651 95 710 1310
21 356 675 96 712 1314
22 369 696 97 714 1317
23 380 716 98 716 1321
24 391 736 99 718 1324
25 402 755 100 720 1328
26 412 774 A
API Project 44, October 31, 1972 is believed to have provided the original normal
27 422 791
paraffin boiling point data that are listed in Table 1. However, over the years some
28 431 808
of the data contained in both API Project 44 (Thermodynamics Research Center
29 440 824
Hydrocarbon Project) and Test Method D6352 have changed and they are no
30 449 840
longer equivalent. Table 1 represents the current normal paraffin boiling point
31 458 856
values accepted by Subcommittee D02.04 and found in all test methods under the
32 466 870
jurisdiction of Section D02.04.0H.
33 474 885 B
Test Method D6352 has traditionally used n-paraffin boiling points rounded to the
34 481 898
nearest whole degree for calibration. The boiling points listed in Table 1 are correct
35 489 912
to the nearest whole number in both degrees Celsius and degrees Fahrenheit.
36 496 925
However, if a conversion is made from one unit to the other and then rounded to
37 503 937
a whole number, the results will not agree with the table values for a few carbon
38 509 948 numbers. For example, the boiling point of n-heptane is 98.425°C, which is
39 516 961 correctly rounded to 98°C in the table. However, converting 98.425°C gives
40 522 972 209.165°F, which rounds to 209°F, while converting 98°C gives 208.4°F, which
41 528 982 rounds to 208°F. Carbon numbers 2, 4, 7, 8, 9, 13, 14, 15, 16, 25, 27, and 32 are
42 534 993 affected by rounding.
43 540 1004
44 545 1013
45 550 1022
46 556 1033
47 561 1042
48 566 1051
49 570 1058
50 575 1067
51 579 1074
52 584 1083
53 588 1090
54 592 1098
55 596 1105
56 600 1112
57 604 1119
58 608 1126
59 612 1134
60 615 1139
61 619 1146
62 622 1152
63 625 1157
64 629 1164
65 632 1170
66 635 1175 FIG. 1 Chromatogram of C5 to C44 Plus Polywax 655 Used to Ob-
67 638 1180 tain Retention Time/Boiling Point Curve Using a 100 % Dimethyl-
68 641 1186 polysiloxane Stationary Phase
69 644 1191
70 647 1197
71 650 1202
72 653 1207 8.1.2 Attach one of the column specified in Table 4 to the
73 655 1211
74 658 1216
detector inlet by ensuring that the end of the column terminates
75 661 1222 as close as possible to the FID jet tip. Follow the instructions
in Practice E1510.

Copyright by ASTM Int'l (all rights reserved); 4

 D6352 − 04 (2009)
TABLE 3 Typical Gas Chromatographic Conditions for the
Simulated Distillation of Petroleum Fractions in the Boiling
Range from 174 to 700°C
Instrument a gas chromatography equipped with an on-column
or temperature programmable vaporizing injector
(PTV)

Column capillary, aluminum clad fused silica

5 m × 0.53 mm id
film thickness 0.1 microns
of a 100 % dimethylpolysiloxane stationary phase

Flow conditions UHP helium at 18 ml/min (constant flow)

Injection temperature oven-track mode

Detector flame ionization;

air 400 ml/min, hydrogen 32 ml/min
make-up gas, helium at 24 ml/min
FIG. 2 Scale-Expanded Chromatogram of Latest Eluting Peaks temperature: 450°C
Showing C76 to C98 Normal Paraffins on a 100 % Dimethylpolysi- range: 2E5
loxane Stationary Phase
Oven program initial oven temperature 50°C,
initial hold 0 min,
A
TABLE 2 Test Method D6352 Reference Material 5010 program rate 10°C/min,
% OFF Average, 95.5% CI, °F Average, 95.5% CI, °C final oven temperature 400°C,
°F Allowable °C Allowable final hold 6 min,
Difference Difference equilibration time 5 min.

IBP 801 16 428 9 Sample size 0.5 µL

5 891 5 477 3
10 918 5 493 3 Sample dilution 1 weight % in carbon disulfide
15 936 5 502 3
20 950 6 510 3 Calibration dilution 0.5 weight % in carbon disulfide
25 963 6 518 4
30 975 7 524 4
35 987 7 531 4
40 998 8 537 4 TABLE 4 Column Selection for Performing Boiling Range
45 1008 8 543 4 Distribution of Petroleum Distillates in the Range from 174 to
50 1019 8 548 5 700°C by Gas Chromatography
55 1030 8 554 4
60 1040 8 560 4 Capillary Column
65 1051 8 566 4 5 m × 0.53 mm I.D., Polymide or aluminum clad fused silica capillary column
70 1062 8 572 4 with a bonded phase of 100 % dimethylpolysiloxane of 0.1 micron film
75 1073 9 578 5 thickness.
80 1086 8 585 4
85 1099 7 593 4 5 m × 0.53 m I.D., stainless steel columns with a bonded phase of 100 %
90 1116 8 602 4 dimethylpolysiloxane of 0.1 micron film thickness
95 1140 7 616 4
FBP 1213 32 655 18
A
Consensus results obtained from 14 laboratories in 2000.
generate a stable and repeatable chromatographic baseline.
Follow the guidelines outlined in Practice E1510.
8.2 System Performance Specification:
8.1.3 The FID should be periodically inspected and, if 8.2.1 Column Resolution—The column resolution, influ-
necessary, remove any foreign deposits formed in the detector enced by both the column physical parameters and operating
from combustion of silicone liquid phase or other materials. conditions, affects the overall determination of boiling range
Such deposits will change the response characteristics of the distribution. Resolution is, therefore, specified to maintain
detector. equivalence between different systems (laboratories) employ-
8.1.4 If the sample inlet system is heated, a blank analysis ing this test method. Resolution is determined using Eq 1 and
shall be made after a new septum is installed to ensure that no the C50 and C52 paraffins from a calibration mixture analysis
extraneous peaks are produced by septum bleed. At the (or a polywax retention time boiling point mixture). Resolution
sensitivity levels commonly employed in this test method, (R) should be at least two (2) and not more than four (4), using
conditioning of the septum at the upper operating temperature the identical conditions employed for sample analyses.
of the sample inlet system for several hours will minimize this R 5 2 ~ t 2 2 t 1 ! / ~ 1.699 ~ w 2 1w 1 !! (1)
problem. The inlet liner and initial portion of the column shall
be periodically inspected and replaced, if necessary, to remove where:
extraneous deposits or sample residue. t1 = time (s) for the n-C50 peak max,
8.1.5 Column Conditioning—A new column will require t2 = time (s) for the n-C52 peak max,
conditioning at the upper test method operating temperature to w1 = peak width (s), at half height, of the n-C50 peak, and
w2 = peak width (s), at half height, of the n-C52 peak.
reduce or eliminate significant liquid phase bleed to produce or

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 D6352 − 04 (2009)
8.2.2 Detector Response Calibration —This test method initial starting temperature, equilibration time, sample injection
assumes that the FID response to petroleum hydrocarbons is and system start, analysis, and final high temperature hold
proportional to the mass of individual components. This shall time.
be verified when the system is put in service, and whenever any 9.1.1 After chromatographic conditions have been set to
changes are made to the system or operational parameters. meet performance requirements, program the column tempera-
Analyze the response linearity mixture (see 7.6) using the ture upward to the maximum temperature to be used and hold
identical procedure to be used for the analysis of samples (see that temperature for the selected time. Following the analysis
Section 9). Calculate the relative response factor for each sequence protocol, cool the column to the initial starting
n-paraffin (relative to n-tetracontane) in accordance with Prac- temperature.
tice D4626 and Eq 2: 9.1.2 During the cool down and equilibration time, ready
Fn 5 ~ Cn/An! / ~ Cn 2 C40/An 2 C40! (2) the integrator/computer system. If a retention time calibration
is being performed, use the peak detection mode. For samples
where:
and baseline compensation (with or without solvent injection),
Cn = concentration of the n-paraffin in the mixture, use the area slice mode operation. The recommended slice rate
An = peak area of the n-paraffin in the mixture,
for this test method is 1.0 Hz (1 s). Other slice rates may be
Cn-C40 = concentration of the n-tetracontane in the mixture,
used if within the limits from 0.02 to 0.2 % of the retention
and
An-C40 = peak area of the n-tetracontane in the mixture. time of the final calibration component (C90). Larger slice
rates may be used, as may be required for other reasons, if
The relative response factor (Fn) of each n-paraffin shall not provision is made to accumulate (bunch) the slice data to
deviate from unity by more than 65 %. Results of response within these limits prior to determination of the boiling range
factor determinations by one lab are presented in Table 5. distribution.
8.2.3 Column Temperature—The column temperature pro-
9.1.3 At the exact time set by the schedule, inject either the
gram profile is selected such that there is baseline separation
calibration mixture, solvent, or sample into the chromatograph;
between the solvent and the first n-paraffin peak (C10) in the
or make no injection (perform a baseline blank). At the time of
calibration mixture and the maximum boiling point (700°C).
injection, start the chromatograph time cycle and the
n-Paraffin (C90) is eluted from the column before reaching the
integrator/computer data acquisition. Follow the analysis pro-
end of the temperature program. The actual program rate used
tocol for all subsequent repetitive analyses or calibrations.
will be influenced by other operating conditions, such as
Since complete resolution of sample peaks is not expected, do
column dimensions, carrier gas and flow rate, and sample size.
not change the sensitivity setting during the analysis.
Thin liquid phase film thickness and narrower bore columns
may require lower carrier gas flow rates and faster column 9.2 Baseline Blank—A blank analysis (baseline blank) shall
temperature program rates to compensate for sample compo- be performed at least once per day. The blank analysis may be
nent overloading (see 9.3.1). without injection or by injection of an equivalent solvent
8.2.4 Column Elution Characteristics —The column phase volume as used with sample injections, depending upon the
is non-polar and having McReynolds numbers of x = 15–17, y subsequent data handling capabilities for baseline/solvent com-
= 53–57, z = 43–46, u = 65–67, and s = 42–45. pensation. The blank analysis is typically performed prior to
sample analyses, but may be useful if determined between
9. Procedure samples or at the end of a sample sequence to provide
9.1 Analysis Sequence Protocol —Define and use a prede- additional data regarding instrument operation or residual
termined schedule of analysis events designed to achieve sample carry over from previous sample analyses.
maximum reproducibility for these determinations. The sched- NOTE 4—If automatic baseline correction (see Note 2) is provided by
ule shall include cooling the column oven and injector to the the gas chromatograph, further correction of area slices may not be
required. However, if an electronic offset is added to the signal after
baseline compensation, additional area slice correction may be required in
the form of offset subtraction. Consult the specific instrumentation
instructions to determine if an offset is applied to the signal. If the
TABLE 5 Measured Response of the Flame Ionization Detector as algorithm used is unclear, the slice area data can be examined to determine
a Function of Carbon Number for One Laboratory Using a Fused if further correction is necessary. Determine if any offset has been added
Silica Column with 100 % Dimethylpolysiloxane Stationary Phase to the compensated signal by examining the corrected area slices of those
Measured time slices that precede the elution of any chromatographic unretained
Carbon substance. If these corrected area slices (representing the true baseline)
Response Factor
No.
(nC40 = 1.00) deviate from zero, subtract the average of these corrected area slices from
12 0.98 each corrected area slice in the analysis.
14 0.96
17 0.95 9.3 Retention Time versus Boiling Point Calibration—A
20 0.97 retention time versus boiling point calibration shall be per-
28 0.96
32 0.98 formed on the same day that analyses are performed. Inject an
36 0.96 appropriate aliquot (0.2 to 2.0 µL) of the calibration mixture
40 1.00 (see 7.5) into the chromatograph, using the analysis schedule
44 0.98
60 0.97 protocol. Obtain a normal (peak detection) data record to
determine the peak retention times and the peak areas for each

Copyright by ASTM Int'l (all rights reserved); 6

 D6352 − 04 (2009)
component. Collect a time slice area record if a boiling range
distribution report is desired.
9.3.1 Inspect the chromatogram of the calibration mixture
for evidence of skewed (non-Gaussian shaped) peaks. Skew-
ness is often an indication of overloading the sample capacity
of the column, which will result in displacement of the peak
apex relative to non-overloaded peaks. Skewness results ob-
tained by one laboratory are presented in Table 6. Distortion in
retention time measurement and, hence, errors in boiling point
temperature determination will be likely if column overloading
occurs. The column liquid phase loading has a direct bearing
on acceptable sample size. Reanalyze the calibration mixture
using a smaller sample size or a more dilute solution if peak
distortion or skewness is evident.
[Link] Skewness Calculation—Calculate the ratio A/B on
specified peaks in the calibration mixture as indicated by the
designations in Fig. 3. A is the width in seconds of the portion
of the peak eluting prior to the time of the apex peak and
measured at 10 % of peak height (0.10-H), and B is the width
in seconds of the portion of the peak eluting after the time of
the peak apex at 10 % of peak height (0.10-H). This ratio for
the n-pentacontane (normal C50) peak in the calibration mix-
ture shall not be less than 0.5 or more than 2.0. Results of
analysis in one laboratory are presented in Table 6.
9.3.2 Prepare a calibration table based upon the results of
the analysis of the calibration mixture by recording the time of
each peak maximum and the boiling point temperature in °C
FIG. 3 Designation of Parameters for Calculation of Peak Skew-
(or °F) for each component in the mixture. A typical calibration ness
table is presented in Table 7. n-Paraffin boiling point (atmo-
spheric equivalent temperatures) are listed in Table 1. Fig. 1 ranges from 0.2 to 2.0 µL of the diluted sample. The maximum
illustrates a graphic plot of typical calibration data. sample signal amplitude should not exceed the maximum
9.4 Sample Preparation—Sample aliquots are introduced calibration signal amplitude found in 9.3.1. A chromatogram
into the gas chromatograph as solutions in a suitable solvent for round robin sample 95-3 is presented in Fig. 4.
(for example, CS2).
9.4.1 Place approximately 0.1 to 1 g of the sample aliquot
into a screw-capped or crimp-cap vial.
9.4.2 Dilute the sample aliquot to approximately 1 weight %
with the solvent.
9.4.3 Seal (cap) the vial, and mix the contents thoroughly to
provide a homogeneous mixture. It may be necessary to warm
the mixture initially to affect complete solution of the sample.
However, the sample shall be in stable solution at room
temperature prior to injection. If necessary, prepare a more
dilute solution.
9.5 Sample Analysis—Using the analysis sequence protocol,
inject a diluted sample aliquot into the gas chromatograph.
Collect a contiguous time slice record of the entire analysis.
9.5.1 Be careful that the injection size chosen does not
exceed the linear range of the detector. The typical sample size FIG. 4 Chromatogram of Round Robin Sample 95-3 Obtained Us-
ing a Fused Silica Capillary Column with 100 % Dimethylpolysi-
loxane Stationary Phase
TABLE 6 Measured Resolution and Skewness for One Laboratory
Using a Fused Silica Column Coated with a 100 %
Dimethylpolysiloxane Stationary Phase 9.5.2 Ensure that the system’s return to baseline is achieved
Resolution between: nC50 and nC52 3.3 near the end of the run. If the sample chromatogram does not
return to baseline by the end of the temperature program, the
Skewness for nC50 sample apparently has not completely eluted from the columns,
at 10 % of peak height: 1.17
at 50 % of peak height: 1.00 and the sample is considered outside the scope of the test
method.

Copyright by ASTM Int'l (all rights reserved); 7

 D6352 − 04 (2009)
TABLE 7 Typical Calibration Report of Retention Time and 10.4 Repeat 10.2, using the blank run table.
Boiling Points, °C, for Normal Paraffins on 100 %
Dimethylpolysiloxane Stationary Phase 10.5 Verify that the slice width used to acquire the sample
Carbon Boiling Retention Time, chromatogram is the same used to acquire the blank run
No. Point, °C min chromatogram.
nC10 174 0.25
nC12 216 0.58
10.6 Subtract from each slice in the sample chromatogram
nC14 254 1.61 table with its correspondent slice in the blank run chromato-
nC15 271 2.40 gram table.
nC16 287 3.27
nC17 302 4.18 10.7 Offset the corrected slices of the sample chromatogram
nC18 316 5.07 by taking the smallest slice and subtracting it from all the
nC20 344 6.78
nC22 369 8.38 slices. This will zero the chromatogram.
nC24 391 9.84
nC26 412 11.21
10.8 Verify the extent of baseline drift.
nC28 431 12.48 10.8.1 Calculate the average and standard deviation of the
nC30 449 13.67 first five area slices of the chromatogram.
nC32 466 14.79
nC34 481 15.86 10.8.2 Eliminate any of the first five slices that are not
nC36 496 16.88 within one standard deviation of the average and recompute the
nC38 509 17.83 average. This eliminates any area that is due to possible
nC40 522 18.74
nC42 534 19.62 baseline upset from injection.
nC44 545 20.46 10.8.3 Record the average area slice as Initial Baseline
nC46 556 21.26
nC48 566 22.02
Signal.
nC50 575 22.77 10.8.4 Repeat 10.8.1 and 10.8.2 using the last five area
nC52 584 23.47 slices of the chromatogram.
nC54 592 24.15
nC56 600 24.82 10.8.5 Record the average area slice as Final Baseline
nC58 608 25.46 Signal.
nC60 615 26.08 10.8.6 Compare and report the Initial and Final Baseline
nC62 622 26.68
nC64 629 27.25 Signals. These numbers should be similar.
nC66 635 27.81
nC68 641 28.35
10.9 Determine the start of sample elution time.
nC70 647 28.88 10.9.1 Calculate the total area. Add all the corrected slices
nC72 653 29.39 in the table. If the sample to be analyzed has a solvent peak,
nC74 658 29.90
nC76 664 30.39 start counting area from the point at which the solvent peak has
nC78 670 30.86 eluted completely. Otherwise, start at the first corrected slice.
nC80 675 31.31 10.9.2 Calculate the rate of change between each two
nC82 681 31.77
nC84 686 32.22 consecutive area slices, beginning at the slice set in 10.9.1 and
nC86 691 32.64 working forward. The rate of change is obtained by subtracting
nC88 695 33.05 the area of a slice from the area of the immediately preceding
nC90 700 34.25
nC92 704 34.32 slice and dividing by the slice width. The time where the rate
of change first exceeds 0.0001 % per second of the total area
(see 10.9.1) is defined as the start of sample elution time.
10.9.3 To reduce the possibility of noise or an electronic
10. Calculation spike falsely indicating the start of sample elution time, a 3-s
10.1 Load into a table the sample chromatogram slices. slice average can be used instead of a single slice. For noisier
10.2 Perform a slice offset. baselines, a slice average larger than 3 s may be required.
10.2.1 Calculate the average slice offset at start of chro- 10.10 Determine the end of sample elution time by using the
matogram as follows: Calculate the average and standard following algorithm:
deviation of the first five area slices of the chromatogram. 10.10.1 Calculate the sample total area. Add all the cor-
Throw out any of the first five slices that are not within one rected slices in the table starting from the slice corresponding
standard deviation of the average and recompute the average. to the start of sample elution time.
This eliminates any area that is due to possible baseline upset 10.10.2 Calculate the rate of change between each two
from injection. consecutive area slices, beginning at the end of run and
10.2.2 Subtract the average area slice from all the slices of working backwards. The rate of change is obtained by sub-
the sample chromatogram. This will zero the chromatogram. tracting the area of a slice from the area of the immediately
10.3 Load into a table the blank run chromatogram slices. preceding slice and dividing by the slice width. The time where
the rate of change first exceeds 0.00001 % per second of the
NOTE 5—For instruments that compensate the baseline directly at the total area (see 10.10.1) is defined as the end of sample elution
detector producing an electronically corrected baseline, either process the
sample chromatogram directly or do a baseline subtraction. If the
time.
compensation is made by the instrument, 10.4-10.7 may be eliminated and 10.10.3 To reduce the possibility of noise or an electronic
proceed to 10.8. spike falsely indicating the end of sample elution time, a 3-s

Copyright by ASTM Int'l (all rights reserved); 8

 D6352 − 04 (2009)
slice average can be used instead of a single slice. For noisier T f 5 A x ·W (4)
baselines, a slice average larger than 3 s may be required.
where:
10.11 Calculate the sample total area. Add all the slices W = slice width,
from the slice corresponding to the start of sample elution time Ax = fraction of the slice that will yield the exact percent,
to the slice corresponding to the end of run. and
10.12 Normalize to area percent. Divide each slice in the Tf = fraction of time that will yield Ax.
sample chromatogram table by the total area (see 10.11) and [Link] Record the exact time where the cumulative area
multiply it by 100. is equal to the X percent of the total area:
10.13 Calculate the Boiling Point Distribution Table: T t 5 T s 1T f (5)
10.13.1 Initial Boiling Point—Add slices in the sample
chromatogram until the sum is equal to or greater than 0.5 %. where:
If the sum is greater than 0.5 %, interpolate (refer to the Ts = fraction of the slice that yields the cumulative percent
algorithm in 10.15.1) to determine the time that will generate up to the slice prior to X,
the exact 0.5 % of the area. Calculate the boiling point Tf = fraction of time that will yield Ax, and
temperature corresponding to this slice time using the calibra- Tt = time where the cumulative area is equal to X percent of
tion table. Use interpolation when required (refer to the the total area.
algorithm in 10.15.2). 10.15.2 Interpolate to determine the exact boiling point
10.13.2 Final Boiling Point—Add slices in the sample given the retention time corresponding to a cumulative slice
chromatogram until the sum is equal to or greater than 99.5 %. area.
If the sum is greater than 99.5 %, interpolate (refer to the [Link] Compare the given time against each retention
algorithm in 10.15.1) to determine the time that will generate time in the calibration table. Select the nearest standard having
the exact 99.5 % of the area. Calculate the boiling point
a retention time equal to or larger than the interpolation time.
temperature corresponding to this slice time using the calibra-
(Warning— The retention time table shall be sorted in
tion table. Use interpolation when required (refer to the
ascending order.)
algorithm in 10.15.2).
10.13.3 Intermediate Boiling Point—For each point be- [Link] If the interpolation time is equal to the retention
tween 1 % and 99 %, find the time where the cumulative sum time of the standard, record the corresponding boiling point.
is equal to or greater than the area percent being analyzed. As [Link] If the retention time is not equal to a retention
in 10.13.1 and 10.13.2, use interpolation when the accumulated time of the standard (see 9.3), interpolate the boiling point
sum exceeds the area percent to be estimated (refer to the temperature as follows:
algorithm in 10.15.1). Use the calibration table to assign the [Link] If the interpolation time is less than the first
boiling point. retention time in the calibration table, then extrapolate using
10.14 Report Results: the first two components in the table:
10.14.1 Print the boiling point distribution table. BPx 5 m 1 · ~ RTx 2 RT1 ! 1BP1 (6)
10.14.2 Print the running conditions, slice width, and start where:
and end of analysis time.
m1 = (BP2 – BP1) / (RT2 – RT1),
10.15 Calculation Algorithms: BPx = boiling point extrapolated,
10.15.1 Calculations to determine the exact point in time RTx = retention time to be extrapolated,
that will generate the X percent of total area, where X = 0.5, 1, RT1 = retention time of the first component in the table,
2, ..., 99.5 %. BP 1 = boiling point of the first component in the table,
[Link] Record the time of the slice just prior to the slice RT2 = retention time of the second component in the table,
that will generate a cumulative slice area larger than the X and
BP2 = boiling point of the second component in the table.
percent of the total area. Let us call this time, Ts, and the
cumulative area at this point, Ac. [Link] If the interpolation time is between two retention
[Link] Calculate the fraction of the slice required to times in the calibration table, then interpolate using the upper
produce the exact X percent of the total area: and lower standard components:
X 2 Ac BPx 5 m u · ~ RTx 2 RTl ! 1BPl (7)
Ax 5 (3)
A c11 2 A c
where:
where: mu = (BPu – BPl) / (RTu – RTl),
Ax = fraction of the slice that will yield the exact percent, BPx = boiling point interpolated,
Ac = cumulative percent up to the slice prior to X, RTx = retention time to be interpolated,
Ac+1 = cumulative percent up to the slice right after X, and RTl = retention time of the lower bound component in the
X = desired cumulative percent. table,
BPl = boiling point of the lower bound component in the
[Link] Calculate the time required to generate the frac-
table,
tion of area Ax:

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 D6352 − 04 (2009)

RTu = retention time of the upper bound component in the operation of the test method, exceed the values presented in
table, and Table 8 in only one case in twenty.
BPu = boiling point of the upper bound component in the 12.1.2 Reproducibility—The differences between two single
table. and independent results obtained by different operators work-
ing in different laboratories on identical test material would, in
[Link] If the interpolation time is larger than the last
the long run, in the normal and correct operation of the test
retention time in the calibration table, then extrapolate using
method, exceed the values presented in Table 8 in only one
the last two standard components in the table:
case in twenty.
BPx 5 m n · ~ RTx 2 RTn21 ! 1BPn21 (8)
12.2 Bias—Because the boiling point distribution can be
where: defined only in terms of a test method, no bias for these
mn = (BPn – BPn–1) / (RTn – RTn–1), procedures in Test Method D6352 for determining the boiling
BPx = boiling point extrapolated, range distribution of heavy petroleum fractions by gas chro-
RTx = retention time to be extrapolated, matography have been determined.
RTn–1 = retention time of the standard component eluting 12.2.1 A rigorous, theoretical definition of the boiling range
prior to the last component in the calibration table, distribution of petroleum fractions is not possible due to the
BPn–1 = boiling point of the standard component eluting complexity of the mixture as well as the unquantifiable
prior to the last component in the calibration table, interactions among the components (for example, azeotropic
RTn = retention time of the last standard component in the behavior). Any other means used to define the distribution
calibration table, and would require the use of a physical process, such as a
BPn = boiling point of the last standard component in the conventional distillation or gas chromatographic characteriza-
calibration table. tion. This would therefore result in a method-dependent
definition and would not constitute a true value from which
11. Report
bias can be calculated.
11.1 Report the temperature to the nearest 0.5°C (1°F) at
1 % intervals between 1 and 99 % and at the IBP (0.5 %) and 13. Keywords
the FBP (99.5 %). Other report formats based upon users’ 13.1 boiling range distribution; distillation; gas chromatog-
needs may be employed. raphy; petroleum; petroleum distillate fractions; simulated
distillation
NOTE 6—If a plot of the boiling point distribution curve is desired, use
graph paper with uniform subdivisions and use either retention time or TABLE 8 Repeatability and Reproducibility of Temperatures As a
temperature as the horizontal axis. The vertical axis will represent the Function of Percent Recovered Using a 100 %
sample boiling range distribution from 0 to 100 %. Plot each boiling point Dimethylpolysiloxane Stationary Phase Column
temperature against its corresponding accumulated percent slice area.
Draw a smooth curve connecting the points. Mass % Repeatability, Reproducibility,
Recovered °C (°F) °C (°F)
0.5 (IBP) 8.1 (14.6) 49.1 (88.4)
12. Precision and Bias5 2 3.7 (6.7) 15.4 (27.7)
12.1 Precision—The precision of this test method as deter- 5 2.3 (4.1) 9.0 (16.2)
10 2.8 (5.0) 7.1 (12.8)
mined by the statistical examination of the interlaboratory test 20 2.7 (4.9) 6.2 (11.2)
results is as follows: 30 2.4 (4.3) 5.9 (10.6)
12.1.1 Repeatability—The differences between successive 40 2.6 (4.7) 6.0 (10.8)
50 2.7 (4.9) 6.4 (11.5)
test results obtained by the same operator with the same 60 2.4 (4.3) 6.4 (11.5)
apparatus under constant operating conditions on identical test 70 3.0 (5.4) 7.2 (13.0)
material would, in the long run, in the normal and correct 80 3.0 (5.4) 7.8 (14.0)
90 3.4 (6.1) 10.5 (18.9)
95 4.7 (8.5) 14.3 (25.7)
98 6.3 (11.3) 21.8 (39.2)
5
Supporting data have been filed at ASTM International Headquarters and may 99.5 (FBP) 13.9 (25.0) 38.1 (68.6)
be obtained by requesting Research Report RR:D02-1445.

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 D6352 − 04 (2009)
APPENDIXES

(Nonmandatory Information)

X1. BOILING POINT BIASES OF NON-PARAFFINIC HYDROCARBONS

X1.1 By definition and convention, the basis for retention

time versus boiling point for calibration of correlation in
ASTM simulated distillation procedures are atmospheric
equivalent boiling points of normal paraffin. In this high
temperature simulated distillation procedure, the bases of these
boiling points are the extrapolated data from API project 44
tables (see Table 1). The normal paraffins calibration blends
consist of mixtures of normal paraffins plus an admixture of
Polywax 655, which has been obtained from the Petrolyte
Corporation. There are apparent discrepancies in the measured
versus known boiling points of the non-normal model com-
pounds when compared with the normal paraffin hydrocarbon
curve plotted on the same basis. For a 100 % dimethylpolysi-
loxane stationary phase, data for several non-normal paraffin
hydrocarbon model compounds whose boiling points are
known are presented in Table X1.1. The measured boiling
points were obtained by using a normal paraffin versus reten-
tion time calibration curve to convert the retention times of the
model compounds to a corresponding temperature. These data
demonstrate significant differences between known and mea-
sured boiling points, especially for the multi-ring aromatics
and heteroaromatic compounds. The known or true boiling
point versus retention times of the normal paraffins and the
non-normal paraffin hydrocarbons are presented in Fig. X1.1.
A significant divergence of these curves is evident.
X1.2 In the round robin study carried out recently in support FIG. X1.1 Aromatics and Other Non-Normal Paraffins Deviate Sig-
of this procedure, three columns containing the following nificantly from Normal-Paraffins on 100 % Dimethylpolysiloxane
Stationary Phase

TABLE X1.1 Comparison of Known and Measured Boiling Points liquid phases were evaluated: (1) 100 % dimethylpolysiloxane,
of “Non-Normal Paraffinic” Hydrocarbons Based on Normal (2) polycarbonate-siloxane, (3) (50 % Phenyl) methylpolysi-
Paraffin Calibration Curve Using a 100 % Dimethylpolysiloxane loxane.
Boiling Points, °C (°F)
Non-Normal Paraffinics Known Measured Difference
X1.2.1 The same model compounds were evaluated in
Toluene 128 (231) 127 (229) –1 (1-2) terms of the differences between the known (true) boiling
Pyridine 132 (240) 121 (218) –12 (–22) points and the measured boiling points using the specified
p-Xylene 157 (282) 155 (279) –2 (–3)
Cumene 170 (306) 167 (302) –3 (–5)
column liquid phases were determined. These results are
1-Decene 188 (339) 189 (341) –1 (–2) summarized in Table X1.2. The data indicate that the difference
sec-Butylbenzene 191 (344) 186 (334) –6 (–10) between known and measured boiling points decrease in the
n-Butylbenzene 201 (361) 197 (354) –4 (–7)
trans-Decalin 203 (366) 193 (347) –11 (–19)
order of 100 % dimethylpolysiloxane < polycarbonate-siloxane
cis-Decalin 212 (382) 203 (365) –9 (–17) < (50 % Phenyl) methylpolysiloxane. The comparisons of the
1-Dodecene 231 (416) 231 (416) 0 (0) boiling point/retention times of the model compounds and the
Naphthalene 236 (424) 217 (390) –19 (–34)
2-Methylnaphthalene 259 (466) 238 (429) –21 (–38) normal paraffins are presented in Figs. X1.2-X1.4. These data
1-Methylnaphthalene 263 (473) 240 (432) –23 (–41) illustrate the differences between model compounds and nor-
Indole 272 (489) 241 (434) –31 (–55) mal paraffin curves as a function of column liquid phase. As
Acenaththene 297 (534) 268 (483) –28 (–51)
1-Octadecene 332 (598) 333 (599) +1 (+1) illustrated in Fig. X1.4, the differences between the normal
Dibenzothiophene 350 (630) 307 (553) –43 (–77) paraffins (•) and the model compound (h) curves are essen-
Phenanthrene 357 (642) 311 (560) –46 (–82) tially indistinguishable for the (50 % Phenyl) methylpolysilox-
Anthracene 359 (647) 312 (561) –48 (–86)
Acridine 364 (655) 313 (563) –51 (–92) ane phase column. These results suggest that for highly
Pyrene 413 (743) 351 (631) –62 (–112) aromatic systems a significant difference between simulated
Triphenylene 442 (796) 391 (703) –52 (–93) distillation and physical distillation would be expected from a
Chrysene 465 (837) 391 (703) –74 (–134)
Coronene 543 (977) 484 (871) –59 (–106) 100 % dimethylpolysiloxane column (Fig. X1.2). On average,
these differences among liquid phases are presented in Table

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 D6352 − 04 (2009)
TABLE X1.2 Differences in Temperatures Relative to Published
Boiling Points on Non-Normal Paraffin Hydrocarbons Using
Normal Paraffins As Calibrants for Several Column Stationary
Phases
Temperature Differences on the Following Stationary
Phases, °C (°F)
100 % Poly- (50 % Phenyl)
Boiling Dimethyl- Carborane- Methyl
Compound Point Polysiloxane Siloxane Polysiloxane
Toluene 128 (231) –1 (–2) 8 (14) ...
Pyridine 132 (240) –12 (–22) 9 (16) ...
p-Xylene 157 (282) –2 (–3) 4 (8) ...
Cumene 170 (306) –3 (–5) 3 (6) 22 (39)
1-Decene 188 (339) 1 (2) 2 (3) 5 (9)
Sec-Butyl Benzene 191 (344) –6 (–10) 2 (3) 12 (21)
n-butyl Benzene 201 (361) –4 (–7) 3 (6) 11 (20)
Trans Decalin 203 (366) –11 (–19) –2(–4) ...
1-Dodecene 231 (416) 0 (0) 1 (2) –9 (–16)
Naphthalene 236 (424) –19 (–34) –4 (–8) 17 (31)
2-Methylnaphthalene 259 (466) –21 (–37) –5 (–9) 17 (30)
1-Methylnaphthalene 263 (473) –23 (–41) –6 (–11) 18 (32)
Indole 272 (489) –31 (–55) –21 (–37) 18 (32)
Acenaphthene 297 (534) –28 (–51) –11 (–19) 20 (36)
1-Octadecene 332 (598) 1 (1) 1 (2) 7 (13)
Dibenzothiaphene 350 (630) –43 (–77) –21 (–38) 20 (36)
Phenathrene 357 (642) –46 (–82) –23 (–42) 12 (21)
Anthracene 359 (647) –48 (–86) –26 (–46) 10 (18)
Acridine 413 (743) –62 (–112) –36 (–65) 7 (12)
Pyrene 413 (743) –62 (–112) –36 (–65) –1 (–2)
Tryphenylene 442 (796) –52 (–93) –25 (–45) 7 (13)
Chrysene 465 (837) –74 (–134) –48 (–87) –14 (–25)
Coronene 543 (977) –59 (–106) –23 (–42) 6 (10)
FIG. X1.3 Comparison of Measured Boiling Points of Normal Par-
affins (•) and Non Paraffinic Hydrocarbons (h) Obtained on Poly-
carboranesiloxane Column

X1.3 The differences were obtained from data on unsubsti-

tuted aromatics. Aromatic compounds typically found in pe-
troleum have multiple alkyl substituents. Such aromatics are
expected to have smaller differences than unsubstituted aro-
matics. These data also suggest that a boiling point versus
retention time relationship for calibration may best be served
by an aromatics or substituted aromatics basis, or both, rather
than a normal paraffin hydrocarbon basis (as indicated in
X1.1). However, there are insufficient alkyl by substituted
aromatics available in pure form with established boiling
points to test this hypothesis.
X1.4 In the recent round robin, two samples, in particular,
illustrate potential differences among columns. Round robin
samples HTSD-95-1 represents a refined base oil in which the
major amounts of aromatic components were removed. HTSD-
95-6 represents a heavy distillate fraction from the same crude
source prior to aromatic component removal. The simulated
distillation chromatograms on the HT-95-1 sample (basestock)
using both a 100 % dimethylpolysiloxane and (50 % Phenyl)
methylpolysiloxane stationary phases are presented in Fig.
X1.5. These curves do not illustrate a significant difference
FIG. X1.2 Comparison of Measured Boiling Points of Normal Par- between the two columns. The grand average simulated distil-
affins (•) and Non-Normal Paraffinic Hydrocarbons (h) Obtained lation data for this sample are presented in Table X1.4. These
on a Methylsilicone Column
results suggest that for low aromatic streams, no significant
difference in results would be expected when using any of
these columns’ liquid phases.
X1.3. These differences decrease in the order of 36°C < 17°C
< +8°C for 100 % dimethylpolysiloxane, polycarbonate- X1.5 In contrast, the simulated distillation chromatograms
siloxane, and (50 % Phenyl) methylpolysiloxane, respectively. of the more aromatic distillate (HTSD-95-6) from the same

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 D6352 − 04 (2009)

FIG. X1.5 High Temperature Simulated Distillation Chromato-

grams of a Refined Base Oil (HTSD-95-1) Obtained on a (50 %
Phenyl) Methylpolysiloxane (Upper) and 100 % Dimethylpolysi-
loxane (Lower) Phases

TABLE X1.4 Comparison of High Temperature Simulated

Distillation Results (Grand Average) Obtained for the Refined
Base Oil (HTSD-95–1) on Three Column Liquid Phases
Temperatures, °C, on
Mass % 100 % (50 % Phenyl)-
Recovered Dimethylpolysiloxane Polycarboranesiloxane Methylpolysiloxane
FIG. X1.4 Comparison of Measured Boiling Points of Normal Par- 0.5 420.5 421.5 424.5
affins (•) and Non-Normal Paraffinic Hydrocarbons (h) Obtained 2 451.5 453.0 457.0
on a (50 % Phenyl) Methylpolysiloxane Column 5 473.0 473.5 477.5
10 491.0 491.5 495.5
20 510.5 511.0 514.5
TABLE X1.3 Average Biases Between Known Boiling Points of 30 526.0 525.5 529.0
Non-Normal Paraffinic Hydrocarbons and Those Measured on 40 538.0 536.5 540.0
Different Column Stationary Phases in the 200°C Plus Range 50 545.5 546.5 550.5
Using HTSD Methodology 60 555.0 556.5 560.0
70 565.0 566.5 570.0
Average Biases 80 575.0 577.0 580.5
Column Stationary Phase °C °F 90 588.5 591.0 594.5
100 % Dimethylpolysiloxane –36 –65 95 599.5 602.5 606.5
Polycarborane Siloxane –17 –31 98 611.5 615.5 619.5
(50 % Phenyl) Methylpolysiloxane +8 +15 99.5 626.5 632.5 636.5

crude sources are presented for the same two columns in Fig.
X1.6 and for the three column phases employed in the round Method D2892 are available to help decide which stationary
robin, the grand average simulated distillation data for HTSD- phase gives the best agreement with physical distillation. The
95-6 are presented in Table X1.5. These data indicate a greater study group also felt that consistency of this test method with
difference in reported temperatures versus yield with the (50 % Test Method D2887, which uses dimethylpolysiloxane station-
Phenyl) methylpolysiloxane stationary phase providing the ary phase, was also an issue. In the absence of good physical
higher boiling points. These results are consistent with differ- distillation data and simulated distillation data for the same
ences in column liquid phases presented in X1.1 and suggest samples obtained by this test method, the test method employ-
that more aromatic or heteroaromatic distillates would be ing dimethylpolysiloxane stationary phase was selected for use
expected to produce significantly different boiling point-yield in this test method. This test method, therefore, does not claim
data when using different column liquid phases. agreement between physical distillation and simulated distilla-
tion. Efforts to resolve this question will continue. When
X1.6 The study group has been trying to obtain samples for successful resolutions of the questions are determined, this test
which good true boiling point data as generated from Test method will be revised accordingly.

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 D6352 − 04 (2009)

FIG. X1.6 High Temperature Simulate Distillation Chromatogram of a Heavy Distillate Fraction (HTSD-95-6) Obtained on a (50 % Phenyl)
Methylpolysiloxane and 100 % Dimethylpolysiloxane

TABLE X1.5 Comparison of High Temperature Simulated

Distillation Results (Grand Average) Obtained for the Heavy
Distillate Fraction (HTSD-95–6) on Three Column Stationary
Phases
Temperatures, °C, on
Mass % 100 % (50 % Phenyl)-
Recovered Dimethylpolysiloxane Polycarboranesiloxane Methylpolysiloxane
0.5 394.0 402.0 399.0
2. 435.0 445.0 448.5
5. 462.5 471.5 477.5
10 482.5 491.0 498.0
20 504.0 511.5 519.0
30 518.0 526.0 533.5
40 529.5 537.0 544.5
50 539.5 547.0 555.0
60 549.0 557.0 565.0
70 559.0 566.5 574.5
80 570.0 577.5 585.5
90 584.5 592.5 601.5
95 595.5 605.5 615.0
98 608.5 620.5 631.5
99.5 625.5 642.5 652.0

X2. CALCULATION ALGORITHM

INTRODUCTION

Test Method D6352 contains instructions on performing the calculations. This appendix is provided
in order to give detailed programming information as well as to unify the algorithms used here and
in Test Method D2887.

X2.1 Required Starting Elements X2.1.2.1 The analysis conditions for blank and sample must
X2.1.1 Sample Data Array, N Area Slices—The data must be identical through the point where sample analysis is
be collected at a minimum sampling frequency of 5 to 10 Hz terminated.
(that is, slice width is 0.2 to 0.1 s). In addition, the slice width X2.1.2.2 The number of slices in the blank array must be
must be such that no sample or solvent elutes in the first 10 to equal to or greater than the number of slices in the sample
20 slices, respectively. chromatogram. If the number of slices in the blank array is
X2.1.2 Blank Data Array, N Area Slices—The slice width greater than the number of slices in the sample array, then drop
for the blank and sample runs must be identical. (A blank data the extra slices in the blank array. This situation could occur if
array may not be necessary if electronic baseline compensation a blank run extended beyond the point where the sample
is used. See X2.2.1.) analysis was terminated.

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 D6352 − 04 (2009)
X2.1.3 Retention Times, n-Paraffıns—The retention time of X2.5 Determine Start of Sample Elution Time
each n-paraffin in the calibration mixture must be obtained X2.5.1 Starting at the slice corresponding to the solvent
from a processed (peak) data file from the analysis of the exclusion time (or the first slice if no solvent was used) and
calibration mixture, run under identical conditions as the working towards the end of the data array, determine where the
samples and blank. rate of change per second between two consecutive slices first
X2.1.4 Boiling Points of n-Paraffıns—The boiling point of exceeds 0.00001 % of the total chromatogram area (see
each n-paraffin in the calibration mixture (to the nearest whole X2.4.2).
degree Celsius or Fahrenheit) can be obtained from Table 1 of X2.5.1.1 For determining the start of sample elution, the
this test method. rate of change is calculated by subtracting the area of a slice
from the area of the immediately following slice and dividing
X2.1.5 Solvent Exclusion Time—The solvent exclusion time by the slice width in seconds.
is that time when the signal has returned to baseline after X2.5.1.2 If (<slice>N + 1 – <slice>N)/(slice width) > 1E-7 ×
elution of the solvent. This parameter is used to exclude area total chromatogram area, then take slice N + 1 as the start of
due to the solvent used, if any. If a solvent is used, the detector sample slice (see X2.2).
signal must return to baseline before any sample components
X2.5.2 Print the retention time corresponding to the start of
start to elute.
sample elution.
X2.2 Subtract Blank from Sample (see Note X2.1)
X2.6 Determine the End of Sample Elution Time
X2.2.1 Subtract each blank area slice from the exactly X2.6.1 Starting at the last slice in the data array and working
corresponding sample area slice. This corrects the sample area toward the start of sample, determine where the rate of change
slice from the blank. (Warning—Automatic baseline compen- per second between two consecutive slices first exceeds
sation is available on many instruments and is allowed by this 0.00001 % of the total chromatogram area (see X2.4.2).
test method. However, automatic baseline compensation may X2.6.1.1 For determining the end of sample elution, the rate
not give the same results as slice-by-slice blank subtraction. On of change is calculated by subtracting the area of a slice from
some instruments using automatic baseline compensation, the the area of the immediately preceding slice and dividing by the
compensated baseline has been observed to exhibit an anoma- slice width in seconds.
lous feature at or near the point in the chromatogram where the X2.6.1.2 If (<slice>N – 1 – <slice>N)/(slice width) > 1E-7 ×
programmed oven temperature reaches maximum and is held total chromatogram area, then take slice N – 1 as the end of
for some period of time. The anomalous feature appears as a sample slice (see X2.2).
slow rise in baseline, followed by a relatively sharp decrease,
followed by a level baseline. While the magnitudes of the X2.6.2 Print the retention time corresponding to the end of
anomalies observed have been very small (only a few pico- sample elution.
amps), the slope of the sharp decrease may be sufficient to meet NOTE X2.2—The determination of the start and end of sample elution
the criterion for determining the end of sample elution. In such as determined by the slope of the consecutive slices may differ according
an event, this false triggering of the end of sample criterion will to sample properties. Thus, the sensitivity level may require adjustment.
result in erroneously high values for the FBP. If false triggering X2.7 Calculate Total Corrected Sample Area
occurs and cannot be eliminated, the user should disable
X2.7.1 Sum the corrected area slices from the start of
automatic baseline compensation and perform blank subtrac-
sample slice (see X2.5.1.2) to the end of sample slice (see
tions as described in this appendix.)
X2.6.1.2).
NOTE X2.1—If the data was acquired on an instrument using automatic X2.7.2 Designate this sum as the total corrected sample
baseline compensation, skip X2.2. In this case, the zeroed sample data
array contains the corrected area slices to be used in subsequent calcula-
area, and save it for subsequent calculations.
tions.
X2.8 Normalize to Area Percent
X2.3 Zero the Data Slices X2.8.1 Beginning at the start of sample slice (see X2.5.1.2)
and continuing to the end of sample slice (see X2.6.1.2), divide
X2.3.1 Calculate the average of the first 10 to 20 (5 to 10 each corrected area slice by the total corrected sample area (see
Hz) area slices of the blank-subtracted data array. X2.7.2) and multiply by 100.
X2.3.2 Subtract the average slice area (X2.3.1) from each X2.8.2 Save these normalized area percents in an array for
area slice in the blank-subtracted data array. Set negative subsequent calculations.
numbers to zero.
X2.9 Find Retention Time Corresponding to Percent Off
X2.4 Calculate Total Chromatogram Area X2.9.1 For each X (where X = 0.5, 1, 2, ..., 98, 99.5), find the
retention time corresponding to X percent off.
X2.4.1 Starting at the first slice (or the solvent exclusion
X2.9.1.1 Beginning with the start of sample slice and
time if a solvent is used), sum all of the area slices through the
working toward the end of sample slice, determine the slice
last slice.
(designated N + 1 in the equations) at which the cumulative
X2.4.2 Designate this sum as the total chromatogram area. area percent first equals or exceeds X.

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 D6352 − 04 (2009)
NOTE X2.3—The cumulative area percent of a given slice is the sum of X2.10.1.1 Find the pair of calibration compound retention
the normalized area percents from the start of sample slice through the times that are closest to and bracket the percent off retention
given slice.
time of interest.
X2.9.1.2 For the slice (N + 1) determined above, the
X2.10.1.2 Calculate the boiling point corresponding to the
following inequality should hold;
percent off retention time as follows:
CAN # X # CAN11 (X2.1)
BPi 5 ~~~ BP2 2 BP1 ! / ~ RT2 2 RT1 !! 3 ~ RTi 2 RT1 !! 1BP1
CAN = the cumulative area percent from start of sample (X2.4)
slice through slice N , and
CAN + 1 = the cumulative area percent through slice N + 1. BPi = boiling point for i percent off,
RTi = retention time for i percent off,
X2.9.1.3 Calculate the fraction (f) of normalized area per- RT1 = retention time of calibration compound immediately
cent in slice (N + 1) needed to give exactly X percent off as preceding RTi,
follows: RT2 = retention time of calibration compound immediately
f 5 ~ X 2 CAN ! /A N11 (X2.2) following RTi ,
BP1 = boiling point of compound at RT1, and
AN + 1 = the normalized area percent (not cumulative) of BP2 = boiling point of compound at RT2.
slice N + 1. NOTE X2.4—A report giving percent off at selected boiling point
X2.9.1.4 The retention time corresponding to X percent off intervals can be calculated in an analogous manner.
(RTX) is the retention time of the fractional slice (N + f) and is
calculated as follows: X2.11 Reporting Results
RTX 5 ~ N1f ! 3 slice width (X2.3) X2.11.1 Report the IBP, the temperatures corresponding to 1
X2.10 Convert Retention Times to Boiling Points to 99 % off, and the FBP to the nearest whole degree
Fahrenheit or nearest half a degree Celsius.
X2.10.1 For each retention time found in X2.9.1, calculate
the boiling point equivalent to that retention time.

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