Astm Astm d2887 PDF

Designation: D2887 – 08
Designation: 406
Standard Test Method for

Boiling Range Distribution of Petroleum Fractions by Gas
Chromatography1, 2
This standard is issued under the fixed designation D2887; 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.
This standard has been approved for use by agencies of the Department of Defense.
1. Scope* D86 Test Method for Distillation of Petroleum Products at

1.1 This test method covers the determination of the boiling Atmospheric Pressure
range distribution of petroleum products. The test method is D1160 Test Method for Distillation of Petroleum Products
applicable to petroleum products and fractions having a final at Reduced Pressure
boiling point of 538°C (1000°F) or lower at atmospheric D2892 Test Method for Distillation of Crude Petroleum
pressure as measured by this test method. This test method is (15-Theoretical Plate Column)
limited to samples having a boiling range greater than 55.5°C D3710 Test Method for Boiling Range Distribution of
(100°F), and having a vapor pressure sufficiently low to permit Gasoline and Gasoline Fractions by Gas Chromatography
sampling at ambient temperature. D4057 Practice for Manual Sampling of Petroleum and
Petroleum Products
NOTE 1—Since a boiling range is the difference between two tempera- D4626 Practice for Calculation of Gas Chromatographic
tures, only the constant of 1.8°F/°C is used in the conversion of the
temperature range from one system of units to another.
Response Factors
D6708 Practice for Statistical Assessment and Improvement
1.2 This test method is not to be used for the analysis of of Expected Agreement Between Two Test Methods that
gasoline samples or gasoline components. These types of Purport to Measure the Same Property of a Material
samples must be analyzed by Test Method D3710. E260 Practice for Packed Column Gas Chromatography
1.3 The values stated in SI units are to be regarded as E355 Practice for Gas Chromatography Terms and Rela-
standard. The inch-pound units given in parentheses are for tionships
information only. E516 Practice for Testing Thermal Conductivity Detectors
1.4 This standard does not purport to address all of the Used in Gas Chromatography
safety concerns, if any, associated with its use. It is the E594 Practice for Testing Flame Ionization Detectors Used
responsibility of the user of this standard to establish appro- in Gas or Supercritical Fluid Chromatography
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. 3. Terminology
3.1 Definitions—This test method makes reference to many
2. Referenced Documents
common gas chromatographic procedures, terms, and relation-
2.1 ASTM Standards:3 ships. Detailed definitions of these can be found in Practices
E260, E355, and E594.
1
This test method is under the jurisdiction of ASTM Committee D02 on 3.2 Definitions of Terms Specific to This Standard:
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee 3.2.1 area slice—the area, resulting from the integration of
D02.04.0H on Chromatographic Distribution Methods. the chromatographic detector signal, within a specified reten-
Current edition approved Dec. 1, 2008. Published January 2009. Originally
approved in 1973. Last previous edition approved in 2006 as D2887–06a. DOI:
tion time interval. In area slice mode (see 6.3.2), peak detection
10.1520/D2887-08. parameters are bypassed and the detector signal integral is
2
This standard has been developed through the cooperative effort between recorded as area slices of consecutive, fixed duration time
ASTM and the Institute of Petroleum, London. The IP and ASTM logos imply that intervals.
the ASTM and IP standards are technically equivalent, but their use does not imply
that both standards are editorially identical. 3.2.2 corrected area slice—an area slice corrected for base-
3
For referenced ASTM standards, visit the ASTM website, www.astm.org, or line offset, by subtraction of the exactly corresponding area
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM slice in a previously recorded blank (non-sample) analysis.
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
*A Summary of Changes section appears at the end of this standard.

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D2887 – 08
3.2.3 cumulative corrected area—the accumulated sum of 6. Apparatus
corrected area slices from the beginning of the analysis through
6.1 Chromatograph—The gas chromatograph used must
a given retention time, ignoring any non-sample area (for
have the following performance characteristics:
example, solvent).
3.2.4 final boiling point (FBP)—the temperature (corre- 6.1.1 Detector—Either a flame ionization or a thermal
sponding to the retention time) at which a cumulative corrected conductivity detector may be used. The detector must have
area count equal to 99.5 % of the total sample area under the sufficient sensitivity to detect 1.0 % dodecane with a peak
chromatogram is obtained. height of at least 10 % of full scale on the recorder under
3.2.5 initial boiling point (IBP)—the temperature (corre- conditions prescribed in this test method and without loss of
sponding to the retention time) at which a cumulative corrected resolution as defined in 9.3.1. When operating at this sensitiv-
area count equal to 0.5 % of the total sample area under the ity level, detector stability must be such that a baseline drift of
chromatogram is obtained. not more than 1 % of full scale per hour is obtained. The
3.2.6 slice rate—the time interval used to integrate the detector must be capable of operating continuously at a
continuous (analog) chromatographic detector response during temperature equivalent to the maximum column temperature
an analysis. The slice rate is expressed in hertz (for example, employed. Connection of the column to the detector must be
integrations or slices per second). such that no temperature below the column temperature exists.
3.2.7 slice time—the time associated with the end of each NOTE 2—It is not desirable to operate a thermal conductivity detector at
contiguous area slice. The slice time is equal to the slice a temperature higher than the maximum column temperature employed.
number divided by the slice rate. Operation at higher temperature generally contributes to higher noise
3.2.8 total sample area—the cumulative corrected area, levels and greater drift and can shorten the useful life of the detector.
from the initial area point to the final area point, where the 6.1.2 Column Temperature Programmer—The chromato-
chromatographic signal is considered to have returned to graph must be capable of linear programmed temperature
baseline after complete sample elution. operation over a range sufficient to establish a retention time of
3.3 Abbreviations: at least 1 min for the IBP and to elute compounds up to a
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3.3.1 A common abbreviation of hydrocarbon compounds is boiling temperature of 538°C (1000°F) before reaching the
to designate the number of carbon atoms in the compound. A upper end of the temperature program. The programming rate
prefix is used to indicate the carbon chain form, while a must be sufficiently reproducible to obtain retention time
subscripted suffix denotes the number of carbon atoms (for repeatability of 0.1 min (6 s) for each component in the
example, normal decane = n-C10; isotetradecane = i-C14). calibration mixture described in 7.8.
6.1.3 Cryogenic Column Cooling—Column starting tem-
4. Summary of Test Method peratures below ambient will be required if samples with IBPs
4.1 The boiling range distribution determination by distilla- of less than 93°C (200°F) are to be analyzed. This is typically
tion is simulated by the use of gas chromatography. A nonpolar provided by adding a source of either liquid carbon dioxide or
packed or open tubular (capillary) gas chromatographic col- liquid nitrogen, controlled through the oven temperature cir-
umn is used to elute the hydrocarbon components of the sample cuitry. Excessively low initial column temperature must be
in order of increasing boiling point. The column temperature is avoided to ensure that the stationary phase remains liquid. The
raised at a reproducible linear rate and the area under the initial temperature of the column should be only low enough to
chromatogram is recorded throughout the analysis. Boiling obtain a calibration curve meeting the specifications of the
points are assigned to the time axis from a calibration curve method.
obtained under the same chromatographic conditions by ana- 6.1.4 Sample Inlet System—The sample inlet system must
lyzing a known mixture of hydrocarbons covering the boiling be capable of operating continuously at a temperature equiva-
range expected in the sample. From these data, the boiling lent to the maximum column temperature employed, or provide
range distribution can be obtained. for on-column injection with some means of programming the
entire column, including the point of sample introduction, up to
5. Significance and Use the maximum temperature required. Connection of the column
5.1 The boiling range distribution of petroleum fractions to the sample inlet system must be such that no temperature
provides an insight into the composition of feedstocks and below the column temperature exists.
products related to petroleum refining processes. The gas 6.1.5 Flow Controllers—The gas chromatograph must be
chromatographic simulation of this determination can be used equipped with mass flow controllers capable of maintaining
to replace conventional distillation methods for control of carrier gas flow constant to 61 % over the full operating
refining operations. This test method can be used for product temperature range of the column. The inlet pressure of the
specification testing with the mutual agreement of interested carrier gas supplied to the gas chromatograph must be suffi-
parties. ciently high to compensate for the increase in column back-
5.2 Boiling range distributions obtained by this test method pressure as the column temperature is raised. An inlet pressure
are essentially equivalent to those obtained by true boiling of 550 kPa (80 psig) has been found satisfactory with the
point (TBP) distillation (see Test Method D2892). They are not packed columns described in Table 1. For open tubular
equivalent to results from low efficiency distillations such as columns, inlet pressures from 10 to 70 kPa (1.5 to 10 psig)
those obtained with Test Method D86 or D1160. have been found to be suitable.

D2887 – 08
TABLE 1 Typical Operating Conditions
Packed Columns 1 2 3 4 Open Tubular Columns 5 6 7
Column length, m (ft) 1.2 (4) 1.5 (5) 0.5 (1.5) 0.6 (2) Column length (m) 7.5 5 10
Column outside diameter, mm 6.4 (1/4) 3.2 (1/8) 3.2 (1/8) 6.4 (1/8) Column inner diameter (mm) 0.53 0.53 0.53
(in.)
Liquid phase OV-1 SE-30 UC-W98 SE-30 Stationary phase DB-1 HP-1 HP-1
Percent liquid phase 3 5 10 10 Stationary phase thickness 1.5 0.88 2.65
(m)
Support material SA GB PC PC Carrier gas nitrogen helium helium
Support mesh size 60/80 60/80 80/100 60/80 Carrier gas flow rate, mL/min 30 12 12
Initial column temperature, °C −20 −40 −30 −50 Initial column temperature, °C 40 35 35
Final column temperature, °C 360 350 360 390 Final column temperature, °C 340 350 350
Programming rate,°C/min 10 6.5 10 7.5 Programming rate, °C/min 10 10 20
Carrier gas helium helium N2 helium Detector FID FID FID
Carrier gas flow, mL/min 40 30 25 60 Detector temperature, °C 350 380 370
Detector TC FID FID TC Injector temperature, °C 340 cool on-column cool on-column
Detector temperature, °C 360 370 360 390 Sample size, µL 0.5 1 0.1–0.2
Injection port temperature, °C 360 370 350 390 Sample concentration mass % 25 2 neat
Sample size, µ 4 0.3 1 5
A
Diatoport S; silane treated.
B
Chromosorb G (AW-DMS).
C
Chromosorb P, acid washed.
6.1.6 Microsyringe—A microsyringe is needed for sample 7. Reagents and Materials

introduction. 7.1 Purity of Reagents—Reagent grade chemicals shall be
NOTE 3—Automatic sampling devices or other sampling means, such as used in all tests. Unless otherwise indicated, it is intended that
indium encapsulation, can be used provided: the system can be operated all reagents conform to the specifications of the Committee on
at a temperature sufficiently high to completely vaporize hydrocarbons Analytical Reagents of the American Chemical Society where
with atmospheric boiling points of 538°C (1000°F), and the sampling such specifications are available.4 Other grades may be used,
system is connected to the chromatographic column avoiding any cold provided it is first ascertained that the reagent is of sufficiently
temperature zones. high purity to permit its use without lessening the accuracy of
6.2 Column—Any column and conditions may be used that the determination.
provide separation of typical petroleum hydrocarbons in order 7.2 Liquid Phase for Columns—Methyl silicone gums and
of increasing boiling point and meet the column performance liquids provide the proper chromatographic hydrocarbon elu-
requirements of 9.3.1 and 9.3.3. Successfully used columns tion characteristics for this test method.
and conditions are given in Table 1. 7.3 Solid Support for Packed Columns—Chromatographic
grade diatomateous earth solid support material within a
6.3 Data Acquisition System:
particle size range from 60 to 100 sieve mesh size is recom-
6.3.1 Recorder—A 0 to 1 mV range recording potentiom- mended.
eter or equivalent, with a full-scale response time of 2 s or less 7.4 Carrier Gas—Helium or nitrogen of high purity.
may be used. (Warning—Helium and nitrogen are compressed gases under
6.3.2 Integrator—Means must be provided for determining high pressure.) Additional purification is recommended by the
the accumulated area under the chromatogram. This can be use of molecular sieves or other suitable agents to remove
done by means of an electronic integrator or computer-based water, oxygen, and hydrocarbons. Available pressure must be
chromatography data system. The integrator/computer system sufficient to ensure a constant carrier gas flow rate (see 6.1.5).
must have normal chromatographic software for measuring the 7.5 Hydrogen—Hydrogen of high purity (for example, hy-
retention time and areas of eluting peaks (peak detection drocarbon free) is used as fuel for the flame ionization detector
mode). In addition, the system must be capable of converting (FID). (Warning—Hydrogen is an extremely flammable gas
the continuously integrated detector signal into area slices of under high pressure.)
fixed duration. These contiguous area slices, collected for the 7.6 Air—High purity (for example, hydrocarbon free) com-
entire analysis, are stored for later processing. The electronic pressed air is used as the oxidant for the flame ionization
range of the integrator/computer (for example, 1 V, 10 V) must detector (FID). (Warning—Compressed air is a gas under high
be within the linear range of the detector/electrometer system pressure and supports combustion.)
used. The system must be capable of subtracting the area slice 7.7 Column Resolution Test Mixture—For packed columns,
of a blank run from the corresponding area slice of a sample a nominal mixture of 1 mass % each of n-C16 and n-C18
run.
NOTE 4—Some gas chromatographs have an algorithm built into their 4
Reagent Chemicals, American Chemical Society Specifications, American
operating software that allows a mathematical model of the baseline Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
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profile to be stored in memory. This profile is automatically subtracted listed by the American Chemical Society, see Annual Standards for Laboratory
from the detector signal on subsequent sample analyses to compensate for Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
any baseline offset. Some integration systems also store and automatically and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
subtract a blank analysis from subsequent analytical determinations. MD.

D2887 – 08
TABLE 2 Boiling Points of Normal ParaffinsA,B carbon numbers 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 20, 24, 28, 32,
Carbon Boiling Boiling Carbon Boiling Boiling 36, 40, and 44 have been found to provide a sufficient number of points to
Number Point, °C Point, °F Number Point, °C Point, °F generate a reliable calibration curve.
1 −162 −259 23 380 716 7.8.2 Packed Columns—The final concentration should be
2 −89 −127 24 391 736
3 −42 −44 25 402 755 approximately ten parts of the n-paraffin mixture to one
4 0 31 26 412 774 hundred parts of CS2.
5 36 97 27 422 791 7.8.3 Open Tubular Columns—The final concentration
6 69 156 28 431 808
7 98 209 29 440 825 should be approximately one part of the n-paraffin mixture to
8 126 258 30 449 840 one hundred parts of CS2.
9 151 303 31 458 856 7.9 Reference Gas Oil No. 1—A reference sample that has
10 174 345 32 466 870
11 196 385 33 474 885 been analyzed by laboratories participating in the test method
12 216 421 34 481 898 cooperative study. Consensus values for the boiling range
13 235 456 35 489 912 distribution of this sample are given in Table 3.
14 254 488 36 496 925
15 271 519 37 503 937
16 287 548 38 509 948 8. Sampling
17 302 576 39 516 961
18 316 601 40 522 972 8.1 Samples to be analyzed by this test method must be
19 330 626 41 528 982 obtained using the procedures outlined in Practice D4057.
20 344 651 42 534 993
21 356 674 43 540 1004
8.2 The test specimen to be analyzed must be homogeneous
22 369 695 44 545 1013 and free of dust or undissolved material.
A
API Project 44, October 31, 1972 is believed to have provided the original
normal paraffin boiling point data that are listed in Table 2. However, over the years 9. Preparation of Apparatus
some of the data contained in both API Project 44 (Thermodynamics Research
Center Hydrocarbon Project) and Test Method D2887 have changed, and they are 9.1 Chromatograph—Place in service in accordance with
no longer equivalent. Table 2 represents the current normal paraffin boiling point the manufacturer’s instructions. Typical operating conditions
values accepted by Subcommittee D02.04 and found in all test methods under the
jurisdiction of Section D02.04.0H.
are shown in Table 1.
B
Test Method D2887 has traditionally used n-paraffin boiling points rounded to 9.1.1 When a FID is used, regularly remove the deposits
the nearest whole degree for calibration. The boiling points listed in Table 2 are formed in the detector from combustion of the silicone liquid
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 phase decomposition products. These deposits will change the
rounded to a whole number, the result will not agree with the table value for a few response characteristics of the detector.
carbon numbers. For example, the boiling point of n-heptane is 98.425°C, which is 9.1.2 If the sample inlet system is heated above 300°C
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 (572°F), a blank analysis must be made after a new septum is
rounds to 208°F. Carbon numbers 2, 4, 7, 8, 9, 13, 14, 15, 16, 25, 27, and 32 are installed to ensure that no extraneous detector response is
affected by rounding. produced by septum bleed. At the sensitivity levels commonly
employed in this test method, conditioning of the septum at the
operating temperature of the sample inlet system for several
paraffin in a suitable solvent, such as n-octane, for use in hours will minimize this problem. A recommended practice is
testing the column resolution. (Warning—n-octane is flam- to change the septum at the end of a series of analyses rather
mable and harmful if inhaled.) The calibration mixture speci- than at the beginning of the series.
fied in 7.8.2 may be used as a suitable alternative, provided the 9.2 Column Preparation:
concentrations of the n-C16 and n-C18 components are nomi- 9.2.1 Packed Columns—Any satisfactory method that will
nally 1.0 mass % each. For open tubular columns, use the produce a column meeting the requirements of 9.3.1 and 9.3.3
mixture specified in 7.8.3. can be used. In general, use liquid phase loadings of 3 to 10 %.
7.8 Calibration Mixture—An accurately weighed mixture Condition the column at the maximum operating temperature
of approximately equal mass quantities of n-hydrocarbons to reduce baseline shifts due to bleeding of the column
dissolved in carbon disulfide (CS2). (Warning—Carbon disul- substrate. The column can be conditioned very rapidly and
fide is extremely volatile, flammable, and toxic.) The mixture effectively using the following procedure:
shall cover the boiling range from n-C5 to n-C44, but does not 9.2.1.1 Connect the column to the inlet but leave the
need to include every carbon number (see Note 5). detector end free.
7.8.1 At least one compound in the mixture must have a 9.2.1.2 Purge the column thoroughly at ambient temperature
boiling point lower than the IBP of the sample and at least one with carrier gas.
compound in the mixture must have a boiling point higher than 9.2.1.3 Turn off the carrier gas and allow the column to
the FBP of the sample. Boiling points of n-paraffins are listed depressurize completely.
in Table 2. 9.2.1.4 Seal off the open end (detector) of the column with
7.8.1.1 If necessary, for the calibration mixture to have a an appropriate fitting.
compound with a boiling point below the IBP of the sample, 9.2.1.5 Raise the column temperature to the maximum
propane or butane can be added to the calibration mixture, operating temperature.
non-quantitatively, by bubbling the gaseous compound into the
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9.2.1.6 Hold the column at this temperature for at least 1 h

calibration mixture in a septum sealed vial using a gas syringe. with no flow through the column.
NOTE 5—Calibration mixtures containing normal paraffins with the 9.2.1.7 Cool the column to ambient temperature.

D2887 – 08
TABLE 3 Test Method D2887 Reference Gas Oil No. 1A
Batch 1 Batch 2 Allowable Difference
% Off
°C °F °C °F °C °F
IBP 114 238 115 240 7.6 13.7
5 143 289 151 304 3.8 6.8
10 169 336 176 348 4.1 7.4
15 196 384 201 393 4.5 8.1
20 221 429 224 435 4.9 8.7
25 243 470
30 258 496 259 499 4.7 8.4
35 275 527
40 287 548 289 552 4.3 7.7
45 302 576
50 312 594 312 594 4.3 7.7
55 321 611
60 332 629 332 629 4.3 7.7
65 343 649 343 649
70 354 669 354 668 4.3 7.7
75 364 688 365 690
80 376 709 378 712 4.3 7.7
85 389 732 391 736
90 404 759 407 764 4.3 7.7
95 425 797 428 803 5.0 9.0
FBP 475 887 475 888 11.8 21.2
A
Consensus results for Batch 2 obtained from 30 laboratories in 1995.9
9.2.1.8 Remove the cap from the detector end of the column analysis (see 7.7 and Section 10), and is illustrated in Fig. 1.
and turn the carrier gas back on. Resolution (R) should be at least three, using the identical
9.2.1.9 Program the column temperature up to the maxi- conditions employed for sample analyses:
mum several times with normal carrier gas flow. Connect the R 5 2~t2 2 t1! / [1.699~w2 1 w1!# (1)
free end of the column to the detector.
9.2.1.10 An alternative method of column conditioning that where:
has been found effective for columns with an initial loading of R = resolution,
10 % liquid phase consists of purging the column with carrier t1 = time(s) for the n-C16 peak maximum,
gas at the normal flow rate while holding the column at the t2 = time(s) for the n-C18 peak maximum,
maximum operating temperature for 12 to 16 h, while detached w1 = peak width(s), at half height, of the n-C16 peak, and
from the detector. w2 = peak width(s), at half height, of the n-C18 peak.
9.2.2 Open Tubular Columns—Open tubular columns with 9.3.2 Detector Response Calibration—This test method
cross-linked and bonded stationary phases are available from assumes that the detector response to petroleum hydrocarbons
many manufacturers and are usually pre-conditioned. These is proportional to the mass of individual components. This
columns have much lower column bleed than packed columns. must be verified when the system is put in service, and
Column conditioning is less critical with these columns but whenever any changes are made to the system or operational
some conditioning may be necessary. The column can be parameters. Analyze the calibration mixture using the identical
conditioned very rapidly and effectively using the following procedure to be used for the analysis of samples (see Section
procedure. 10). Calculate the relative response factor for each n-paraffin
9.2.2.1 Once the open tubular column has been properly (relative to n-decane) in accordance with Practice D4626 and
installed into the gas chromatograph and tested to be leak free, Eq 2:
set the column and detector gas flows. Before heating the Fn 5 ~Mn / An! / ~M10 / A10! (2)
column, allow the system to purge with carrier gas at ambient
temperature for at least 30 min. where:
9.2.2.2 Increase the oven temperature about 5 to 10°C per Fn = relative response factor,
minute to the final operating temperature and hold for about 30 Mn = mass of the n-paraffin in the mixture,
min. An = peak area of the n-paraffin in the mixture,
9.2.2.3 Cycle the gas chromatograph several times through M10 = mass of the n-decane in the mixture, and
A10 = peak area of the n-decane in the mixture.
its temperature program until a stable baseline is obtained.
9.3 System Performance Specification: The relative response factor (Fn) of each n-paraffin must not
9.3.1 Column Resolution—The column resolution, influ- deviate from unity (1) by more than 610 %.
enced by both the column physical parameters and operating 9.3.3 Column Elution Characteristics—The column mate-
conditions, affects the overall determination of boiling range rial, stationary phase, or other parameters can affect the elution
distribution. Resolution is therefore specified to maintain order of non-paraffinic sample components, resulting in devia-
equivalence between different systems (laboratories) employ- tions from a TBP versus retention time relationship. If station-
ing this test method. Resolution is determined using Eq 1 and ary phases other than those referenced in 7.3 are used, the
the C16 and C18 paraffins from a column resolution test mixture retention times of a few alkylbenzenes (for example, o-xylene,
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D2887 – 08
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FIG. 1 Column Resolution Parameters
n-butyl-benzene, 1,3,5-triisopropylbenzene, n-decyl-benzene, analysis except no injection is made. A blank analysis must be
and tetradecylbenzene) across the boiling range should be performed at least once per day. The blank analysis is neces-
analyzed to make certain that the column is separating in sary due to the usual occurrence of chromatographic baseline
accordance with the boiling point order (see Appendix X1). instability and is subtracted from sample analyses to remove
any nonsample slice area from the chromatographic data. The
10. Calibration and Standardization
blank analysis is typically performed prior to sample analyses,
10.1 Analysis Sequence Protocol—Define and use a prede- but may be useful if determined between samples or at the end
termined schedule of analysis events designed to achieve of a sample sequence to provide additional data regarding
maximum reproducibility for these determinations. The sched- instrument operation or residual sample carryover from previ-
ule will include cooling the column oven to the initial starting ous sample analyses. Attention must be given to all factors that
temperature, equilibration time, sample injection and system influence baseline stability, such as column bleed, septum
start, analysis, and final upper temperature hold time. bleed, detector temperature control, constancy of carrier gas
10.1.1 After chromatographic conditions have been set to flow, leaks, instrument drift, and so forth. Periodic baseline
meet performance requirements, program the column tempera- blank analyses should be made, following the analysis se-
ture upward to the maximum temperature to be used and hold quence protocol, to give an indication of baseline stability.
that temperature for the selected time. Following the analysis
sequence protocol, cool the column to the initial starting NOTE 6—If automatic baseline correction (see Note 4) is provided by
temperature. the gas chromatograph, further correction of area slices may not be
10.1.2 During the cool down and equilibration time, ready required. However, if an electronic offset is added to the signal after
baseline compensation, additional area slice correction may be required in
the integrator/computer system. If a retention time or detector the form of offset subtraction. Consult the specific instrumentation
response calibration is being performed, use the peak detection instructions to determine if an offset is applied to the signal. If the
mode. For samples and baseline compensation determinations, algorithm used is unclear, the slice area data can be examined to determine
use the area slice mode of integration. The recommended slice if further correction is necessary. Determine if any offset has been added
rate for this test method is 1.0 Hz (one slice per second). Other to the compensated signal by examining the corrected area slices of those
slice rates may be used if within the limits of 0.02 and 0.2 % time slices that precede the elution of any chromatographic unretained
substance. If these corrected area slices (representing the true baseline)
of the retention time of the final calibration component (C44).
deviate from zero, subtract the average of these corrected area slices from
Larger slice rates may be used, as may be required for other each corrected area slice in the analysis.
reasons, if provision is made to accumulate (bunch) the slice
data to within these limits prior to determination of the boiling 10.3 Retention Time Versus Boiling Point Calibration—In
range distribution. order to analyze samples, a retention time versus boiling point
10.1.3 At the exact time set by the schedule, inject either the calibration must be performed. Inject an appropriate aliquot
calibration mixture or sample into the chromatograph; or make (0.2 to 2.0 µL) of the calibration mixture (see 7.8) into the
no injection (baseline blank). At the time of injection, start the chromatograph, using the analysis sequence protocol. Obtain a
chromatograph time cycle and the integrator/computer data normal (peak detection) data record in order to determine the
acquisition. Follow the analysis sequence protocol for all peak retention times and the peak areas for each component.
subsequent repetitive analyses or calibrations. Since complete Collect a time slice area record if a boiling range distribution
resolution of sample peaks is not expected, do not change the report is desired.
detector sensitivity setting during the analysis. 10.3.1 Inspect the chromatogram of the calibration mixture
10.2 Baseline Compensation Analysis—A baseline compen- for evidence of skewed (non-Gaussian shaped) peaks. Skew-
sation analysis, or baseline blank, is performed exactly like an ness is often an indication of overloading the sample capacity

D2887 – 08
FIG. 2 Typical Calibration Curve

--```,``,`,,``,````,``,,,``,,,`,-`-`,,`,,`,`,,`---
of the column that will result in displacement of the peak apex difference in boiling point temperature. In general, the lower
relative to nonoverloaded peaks. Distortion in retention time the sample IBP, the lower will be the starting temperature of
measurement and hence errors in boiling point temperature the analysis. Although extrapolation of the curve at the upper
determination will be likely if column overloading occurs. The end is more accurate, calibration points must bracket the
column liquid phase loading has a direct bearing on acceptable boiling range of the sample at both the low and high ends.
sample size. Reanalyze the calibration mixture using a smaller 10.4 Reference Gas Oil Analysis—The Reference Gas Oil
sample size or a more dilute solution to avoid peak distortion. No. 1 sample is used to verify both the chromatographic and
10.3.2 Prepare a calibration table based upon the results of calculation processes involved in this test method. Perform an
the analysis of the calibration mixture by recording the time of analysis of the gas oil following the analysis sequence proto-
each peak maximum and the boiling point temperature in col. Collect the area slice data and provide a boiling point
degrees Celsius (or Fahrenheit) for every component in the distribution report as in Sections 12 and 13.
mixture. n-Paraffin boiling point temperatures are listed in
Table 2. 10.4.1 The results of this reference analysis must agree with
10.3.3 Plot the retention time of each peak versus the the values given in Table 3 within the range specified by the
corresponding normal boiling point temperature of that com- test method reproducibility (see 14.1.2). If it does not meet the
ponent in degrees Celsius (or Fahrenheit) as shown in Fig. 2. criteria in Table 3, check that all hardware is operating properly
10.3.4 Ideally, the retention time versus boiling point tem- and all instrument settings are as recommended by the manu-
perature calibration plot would be linear, but it is impractical to facturer. Rerun the retention boiling point calibration as de-
operate the chromatograph such that curvature is eliminated scribed in 10.3.
completely. The greatest potential for deviation from linearity 10.4.2 Perform this reference gas oil confirmation test at
will be associated with the lower boiling point paraffins. They least once per day or as often as required to establish
will elute from the column relatively fast and have the largest confidence in consistent compliance with 10.4.1.

D2887 – 08
11. Procedure compounds from previous samples, can preclude the possibility of the
chromatogram returning precisely to the original baseline established prior
11.1 Sample Preparation: to the IBP of the sample. Thus, the most satisfactory procedure is to
11.1.1 The amount of sample injected must not overload the inspect the chromatogram and the area counts at each interval near the end
column stationary phase nor exceed the detector linear range. A of the run to determine the point at which the rate of change per second
narrow boiling range sample will require a smaller amount of the chromatographic signal has reached a constant low value of no
injected than a wider boiling range sample. greater than 0.00001 % of the total area counts. In some rather unusual
11.1.1.1 To determine the detector linear range, refer to cases, a sample may have individual peaks, separated at the end of the run,
which return to baseline between the peaks. In such cases, the total area
Practice E594 for flame ionization detectors or Practice E516
point of the sample obviously is somewhere beyond the last detectable
for thermal conductivity detectors. peak.
11.1.1.2 The column stationary phase capacity can be esti-
mated from the chromatogram of the calibration mixture (see 12.3 Observe the area counts at the start of the run, until the
9.3.2). Different volumes of the calibration standard can be point is reached where the cumulative area count is equal to
injected to find the maximum amount of a component that the 0.5 % of the total area (see 12.2). Mark this point as the IBP of
stationary phase can tolerate without overloading (see 10.3.1). the sample.
Note the peak height for this amount of sample. The maximum 12.4 Divide the cumulative area at each interval between the
sample signal intensity should not exceed this peak height. initial and FBPs by the total area (see 12.2) and multiply by
11.1.2 Samples that are of low enough viscosity to be 100. This will give the cumulative percent of the sample
sampled with a syringe at ambient temperature may be injected recovered at each time interval.
neat. This type of sample may also be diluted with CS2 to 12.5 Tabulate the cumulative percent recovered at each
control the amount of sample injected to comply with 11.1.1. interval and the retention time at the end of the interval. Using
11.1.3 Samples that are too viscous or waxy to sample with linear interpolation where necessary, determine the retention
a syringe may be diluted with CS2. time associated with each percent between 1 and 99.
11.1.4 Typical sample injection volumes are listed below. 12.6 For each percent and its associated retention time,
Packed Columns:
determine the corresponding boiling temperature from the
Stationary Phase Loading, % Neat Sample Volume, µL calibration table (see 10.3.2).
10 1.0
5 0.5 13. Report
Open Tubular Columns:
Film Thickness, µ Neat Sample Volume, µL 13.1 Report the temperature to the nearest 0.5°C (1°F) at
0.8 to 1.5 0.1 to 0.2 1 % intervals between 1 and 99 % and at the IBP (0.5 %) and
1.8 to 3.0 0.1 to 0.5
3.0 to 5.0 0.2 to 1.0 the FBP (99.5 %).
11.2 Sample Analysis—Using the analysis sequence proto- NOTE 9—If a plot of the boiling point distribution curve is desired, use
col, inject a sample aliquot into the gas chromatograph. Collect graph paper with uniform subdivisions and use either retention time or
temperature as the horizontal axis. The vertical axis will represent the
a contiguous time slice area record of the entire analysis. boiling range distribution (0 to 100 %). Plot each boiling temperature
against its corresponding normalized percent. Draw a smooth curve
12. Calculation connecting the points.
NOTE 7—See Appendix X3 for the recommended calculation algo-
rithm.5 14. Precision and Bias 6
12.1 Correct the sample area slices for nonsample detector 14.1 Precision—The precision of this test method as deter-
response by subtracting each blank analysis area slice (as mined by the statistical examination of the interlaboratory test
determined in 10.2) from each sample area slice at the results is as follows:
equivalent slice time. Also see Note 6 regarding automatic 14.1.1 Repeatability—The difference between successive
baseline correction. Sum the corrected area slices to obtain the test results obtained by the same operator with the same
cumulative corrected areas for each time interval during the apparatus under constant operating conditions on identical test
run. material would, in the long run, in the normal and correct
12.2 At the point on the chromatogram where the baseline at operation of the test method, exceed the following values by
the end of the run first becomes steady as the total area point, only one case in twenty (see Table 4).
record the total cumulative corrected area counts. Move back 14.1.2 Reproducibility—The difference between two single
along the chromatogram until a cumulative area equals 99.5 % and independent results obtained by different operators work-
of the total area. Mark this point as the FBP. ing in different laboratories on identical test material would, in
the long run, exceed the following values only one case in
NOTE 8—Location of the FBP may be the most difficult step in this test twenty (see Table 5).
method. Some samples have extremely long tailing end portions due to
gradually decreasing quantities of heavy materials. This fact, coupled with NOTE 10—This precision estimate is based on the analysis of nine
the natural tendency of the chromatographic baseline to rise at the end of samples by 19 laboratories using both packed and open tubular columns.
the run due to septum or column bleed or elution of traces of heavy The range of results found in the round robin are listed in Table 6.
5 6
Supporting data have been filed at ASTM International Headquarters and may Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:D02-1477. be obtained by requesting Research Report RR:D02-1406.
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D2887 – 08
TABLE 4 Repeatability TABLE 6 Round Robin Range of Results
NOTE—x = the average of the two results in °C and y = the average of % Off Range of Results, °C Range of Results, °F
the two results in °F. IBP 112–213 234–415
5% 133–286 271–547
Repeatability
% Off 10 % 139–312 282–594
°C °F 20 % 151–341 304–646
30 % 161–358 322–676
IBP 0.011 x 0.011 (y − 32)
40 % 171–370 340–698
5% 0.0032 (x + 100) 0.0032 (y + 148)
50 % 182–381 360–718
10–20 % 0.8 1.4
60 % 196–390 385–734
30 % 0.8 1.4
70 % 206–401 403–754
40 % 0.8 1.4
80 % 219–412 426–774
50–90 % 1.0 1.8
90 % 233–426 451–799
95 % 1.2 2.2
95 % 241–437 466–819
FBP 3.2 5.8
FBP 274–475 525–887
TABLE 5 Reproducibility gas chromatography has no bias because the boiling range
NOTE—x = the average of the two results in °C and y = the average of distribution can only be defined in terms of a test method.
the two results in °F. 14.2.1 A rigorous, theoretical definition of the boiling range
Reproducibility
distribution of petroleum fractions is not possible due to the
% Off complexity of the mixture as well as the unquantifiable
°C °F
interactions among the components (for example, azeotropic
IBP 0.066 x 0.06 (y − 32)
5% 0.015 (x + 100) 0.015 (y + 148)
behavior). Any other means used to define the distribution
10–20 % 0.015 (x + 100) 0.015 (y + 148) would require the use of a physical process, such as a
30 % 0.013 (x + 100) 0.013 (y + 148) conventional distillation or gas chromatographic characteriza-
40 % 4.3 7.7
50–90 % 4.3 7.7
tion. This would therefore result in a method-dependent
95 % 5.0 9.0 definition and would not constitute a true value from which
FBP 11.8 21.2 bias can be calculated.
15. Keywords
15.1 boiling range distribution; correlation; distillation; gas
14.2 Bias—The procedure in Test Method D2887 for deter- chromatography; petroleum; petroleum fractions; petroleum
mining the boiling range distribution of petroleum fractions by products; simulated distillation
APPENDIXES
(Nonmandatory Information)
X1. BOILING POINTS OF NONPARAFFINIC HYDROCARBONS
X1.1 There is an apparent discrepancy in the boiling point essentially the same. Deviations of simulated distillation boil-
of multiple ring-type compounds. When the retention times of ing points, as estimated from the curve, from actual boiling
these compounds are compared with n-paraffins of equivalent points for a few compounds are shown in Table X1.2. The
atmospheric boiling point, these ring compounds appear to be deviations obtained by plotting boiling points at 10 mm rather
eluted early from methyl silicone rubber columns. A plot than 760 mm are tabulated also. It is apparent that the deviation
showing 36 compounds other than n-paraffins plotted along the is much less at 10 mm pressure. This indicates that the
calibration curve for n-paraffins alone is shown in Fig. X1.1. distillation data produced by gas chromatography closely
The numbered dots are identified in Table X1.1. In this figure, approximates those obtained in reduced pressure distillation.
the atmospheric boiling points are plotted against the observed Since the vapor-pressure-temperature curves for multiple-ring
retention times. If columns containing different percentages of type compounds do not have the same slope or curvature as
stationary phase or different temperature programming rates those of n-paraffins, an apparent discrepancy would exist when
were used, the slope and curvature of the n-paraffin curve (solid
n-paraffin boiling points at atmospheric pressure are used.
line) would change, but the relative relationships would remain
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D2887 – 08
X1.2 However, this discrepancy does not introduce any distillation of three high boiling petroleum fractions is shown
significant error when comparing with laboratory distillation in Table X1.3. The TBP distillations were made on 100
because the pressure must be reduced in such procedures when theoretical plate spinning band columns at 1 mm Hg pressure.
overhead temperatures reach approximately 260°C (500°F) to
prevent cracking of the sample. Thus, distillation data are X1.3 The decanted oil is of particular interest because it
subject to the same deviations experienced in simulated distil- contains a high presence of polycyclic aromatic compounds
lation by gas chromatography. A comparison of data obtained and the high sulfur coker gas oil should contain ring-type sulfur
from TBP distillation with those obtained from simulated compounds and complex olefinic types.
FIG. X1.1 Boiling Point—Retention Time Relationships for Several High-Boiling Multiple-Ring Type Compounds (see Table X1.1)
TABLE X1.1 Compound Identification—Numbered Dots (see Fig. X1.1)

No. Boiling Point, °C (°F) Compound Number Boiling Point, °C (°F) Compound
2 80 (176) benzene 27 227 (441) di-n-amylsulfide
3 84 (183) thiophene 28 234 (453) tri-isopropylbenzene
5 111 (231) toluene 30 241 (466) 2-methylnaphthalene
6 116 (240) pyridine 31 295 (473) 1-methylnaphthalene
8 136 (277) 2,5-dimethylthiophene
9 139 (282) p-xylene 34 254 (489) indole
10 143 (289) di-n-propylsulfide 35 279 (534) acenaphthene
12 152 (306) cumene
13 159 (319) 1-hexahydroindan 38 298 (568) n-decylbenzene
14 171 (339) 1-decene 39 314 (598) 1-octadecene
15 173 (344) sec-butylbenzene
17 178 (352) 2,3-dihydroindene 41 339 (642) phenanthrene
18 183 (361) n-butylbenzene 42 342 (647) anthracene
19 186 (366) trans-decalin
20 194 (382) cis-decalin 44 346 (655) acridine
21 195 (383) di-n-propyldisulfide 45 395 (743) pyrene
23 213 (416) 1-dodecene 47 404 (796) triphenylene
25 218 (424) naphthalene 49 438 (820) naphthacene
26 221 (430) 2,3-benzothiophene 50 447 (837) chrysene
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10
Licensee=BP International/5928366101
D2887 – 08
TABLE X1.2 Deviations of Simulated Distillation Boiling Points From Actual Boiling Points
Boiling Point, °C (°F) Deviations from Actual Boiling Point, °C (°F)
Compound
(760 mm) (760 mm) (10 mm)
Benzene 80 (176) + 3 ( + 6) − 2 (−4)
Thiophene 84 (183) + 4 ( + 7) + 1 ( + 2)
Toluene 111 (231) + 2 ( + 3) − 1 (−2)
p-Xylene 139 (282) 0 (0) + 2 ( + 4)
1-Dodecene 213 (416) 0 (0) 0 (0)
Naphthalene 218 (424) − 11 (−20) − 4 (−8)
2,3-Benzothiophene 221 (430) − 13 (−23) 0 (0)
2-Methylnaphthalene 241 (466) − 12 (−21) − 2 (−3)
1-Methylnaphthalene 245 (473) − 12 (−21) − 1 (−1)
Dibenzothiophene 332 (630) − 32 (−58) − 6 (−10)
Phenanthrene 339 (642) − 35 (−63) − 9 (−16)
Anthracene 342 (647) − 36 (−64) − 8 (−15)
Pyrene 395 (743) − 48 (−87) − 16 (−29)
A
Chrysene 447 (837) − 60 (−108)
A
No data at 10 mm for chrysene.
TABLE X1.3 Distillation of Heavy Gas Oils

Weight Percent Virgin Gas Oil High-Sulfur Coker Gas Oil “Decanted” Oil
OffA TBP,A °C (°F) SD,B °C (°F) TBP, °C (°F) SD, °C (°F) TBP, °C (°F) SD, °C (°F)
C
IBP 230 (446) 215 (419) 223 (433) 209 (409) 190 (374) 176 (348)
10 269 (517) 265 (506) 274 (526) 259 (498) 318 (605) 302 (575)
20 304 (580) 294 (562) 296 (565) 284 (544) 341 (645) 338 (640)
30 328 (622) 321 (610) 316 (600) 312 (593) 357 (675) 358 (676)
40 343 (650) 348 (659) 336 (636) 344 (651) 377 (710) 375 (707)
50 367 (693) 373 (704) 356 (672) 364 (688) 390 (734) 391 (736)
60 394 (742) 409 (749) 377 (710) 386 (727) 410 (770) 409 (768)
70 417 (783) 424 (795) 399 (751) 410 (770) 425 (797) 425 (797)
80 447 (836) 451 (844) 421 (800) 434 (814) 445 (833) 443 (830)
90 ... 488 (910) 462 (863) 467 (872) ... 469 (876)
95 ... 511 (951) 482 (900) 494 (922) ... 492 (918)
100 ... 543 (1009) ... 542 (1007) ... 542 (1007)
A
TBP = True boiling point.
B
SD = Simulated distillation boiling point.
C
IBP = Initial boiling point.
X2. AGREEMENT WITH CONVENTIONAL DISTILLATION
X2.1 Test Method D2892 is the standard for conventional methods has been very good for petroleum products and
distillation of petroleum products. fractions within the scope of this test method.
X2.2 This test method has been compared with Test X2.3 The time required for analysis by this test method is
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Method D2892 on the same samples by a number of labora-

approximately one tenth of that required for Test Method
tories (1-3)7. In all cases, agreement between the two test
D2892, and Test Method D2892 has difficulty establishing the
7
The boldface numbers in parentheses refer to the list of references at the end of IBP and FBP accurately.
this standard.
X3. CALCULATION ALGORITHM
X3.1 Required Starting Elements X3.1.2.1 The analysis conditions for blank and sample must
X3.1.1 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 1 Hz (that is, terminated.
maximum slice width is 1 s). In addition, the slice width must X3.1.2.2 The number of slices in the blank array must be
be such that no sample or solvent elutes in the first five slices. equal to or greater than the number of slices in the sample
X3.1.2 Blank Data Array, N Area Slices—The slice width chromatogram. If the number of slices in the blank array is
for the blank and sample runs must be identical. (A blank data greater than the number of slices in the sample array, then drop
array is not necessary if electronic baseline compensation is the extra slices in the blank array. This situation could occur if
used.)

D2887 – 08
a blank run extended beyond the point where the sample slices 4, 5, and 6 and use the retention time of slice 6. Continue to the end
analysis was terminated. of the data array.
X3.1.3 Retention Times, n-Paraffıns—The retention time of X3.3.4 Calculate the bunched slice width by multiplying the
each n-paraffin in the calibration mixture must be obtained original slice width by the number of slices added to form each
from a processed (peak) data file from the analysis of the bunch.
calibration mixture, run under identical conditions as the
samples and blank. X3.4 Calculate Total Chromatogram Area
X3.1.4 Boiling Points of n-Paraffıns—The boiling points of X3.4.1 Starting at the first slice (or the solvent exclusion
each n-paraffin in the calibration mixture (to the nearest whole time if a solvent is used), sum all of the area slices through the
degree Celsius or Fahrenheit) can be obtained from Table 2 of last bunched slice.
this test method. X3.4.2 Designate this sum as the total chromatogram area.
X3.1.5 Solvent Exclusion Time—The solvent exclusion time
is that time when the signal has returned to baseline after X3.5 Determine Start of Sample Elution Time
elution of the solvent. This parameter is used to exclude area X3.5.1 Starting at the slice corresponding to the solvent
due to the solvent used, if any. If a solvent is used, the detector exclusion time (or the first slice if no solvent was used) and
signal must return to baseline before any sample components working towards the end of the data array, determine where the
start to elute. rate of change per second between two consecutive bunched
slices first exceeds 0.00001 % of the total chromatogram area
X3.2 Subtract Blank from Sample (see Note X3.1) (see X3.4.2).
X3.2.1 Subtract each blank area slice from the exactly X3.5.1.1 For determining start of sample elution, the rate of
corresponding sample area slice. This corrects the sample area change is calculated by subtracting the area of a slice from the
slices for the blank. (Warning—Automatic baseline compen- area of the immediately following slice and dividing by the
sation is available on many instruments and is allowed by this bunched slice width (see X3.3.4) in seconds.
test method. However, automatic baseline compensation may X3.5.1.2 If (<slice>N+1 – <slice>N)/(bunched slice width) >
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not give the same results as slice-by-slice blank subtraction. On 1E-7*total chromatogram area, then take slice N+1 as the start
some instruments using automatic baseline compensation, the of sample slice.
compensated baseline has been observed to exhibit anomalous X3.5.2 Print the retention time corresponding to the start of
features at (or near) the point in the chromatogram where the sample elution.
programmed oven temperature reaches maximum and is held
for some period of time. The anomalous feature appears as a X3.6 Determine End of Sample Elution Time
slow rise in baseline, followed by a relatively sharp decrease, X3.6.1 Starting at the last slice in the data array and working
followed by a level baseline. While the magnitudes of the toward the start of sample, determine where the rate of change
anomalies observed have been very small (only a few pico- per second between two consecutive bunched slices first
amps), the slope of the sharp decrease may be sufficient to meet exceeds 0.00001 % of the total chromatogram area (see
the criterion for determining the end of sample elution. In such X3.4.2).
event, this false triggering of the end of sample criterion will X3.6.1.1 For determining end of sample elution, the rate of
result in erroneously high values for the FBP and other percent change is calculated by subtracting the area of a slice from the
off values near the FBP. If false triggering occurs and can not area of the immediately preceding slice and dividing by the
be eliminated, the user should disable automatic baseline bunched slice width (see X3.3.4) in seconds.
compensation and perform blank subtractions as described in X3.6.1.2 If (<slice>N–1 – <slice>N)/(bunched slice width) >
this appendix.) 1E-7*total chromatogram area, then take slice N-1 as the end
NOTE X3.1—If the data was acquired on an instrument using automatic of sample slice.
baseline compensation, X3.2 must be skipped. In this case, the zeroed and X3.6.2 Print the retention time corresponding to end of
bunched sample data array (see X3.3.3) contains the corrected area slices sample elution.
to be used in subsequent calculations.
X3.7 Calculate Total Corrected Sample Area
X3.3 Zero and Bunch Data Slices
X3.7.1 Sum the corrected area slices from start of sample
X3.3.1 Calculate the average of the first five area slices of slice (see X3.5.1.2) to end of sample slice (see X3.6.1.2).
the blank-subtracted data array. X3.7.2 Designate this sum as the total corrected sample
X3.3.2 Subtract the average slice area (see X3.3.1) from area, and save for subsequent calculations.
each area slice in the blank-subtracted data array. Set negative
numbers to zero. X3.8 Normalize to Area Percent
X3.3.3 If the data sampling frequency was 1.5 Hz or greater, X3.8.1 Starting at the start of sample slice (see X3.5.1.2)
bunch (add together) an integral number of area slices to obtain and continuing to the end of sample slice (see X3.6.1.2), divide
a bunched slice width as close to 1 s as possible. Drop any each corrected area slice by the total corrected sample area (see
extra area slices at the end of the sample data array. X3.7.2) and multiply by 100.
NOTE X3.2—As an example, if data was collected at 3 Hz, add the areas X3.8.2 Save these normalized area percents in an array for
of slices 1, 2, and 3 and use the retention time of slice 3. Add the area of subsequent calculations.

12
D2887 – 08
X3.9 Find Retention Time Corresponding to Percent Off RTX 5 ~N1f!3 bunched slice width (X3.3)
X3.9.1 For each X (where X = 0.5, 1, 2, ... , 98, 99, 99.5),
find the retention time corresponding to X percent off. X3.10 Convert Retention Times to Boiling Points
X3.9.1.1 Beginning with the start of sample slice and X3.10.1 For each retention time found in X3.9.1, calculate
working toward the end of sample slice, determine the slice the boiling point equivalent to that retention time.
(designated N+1 in the equations) at which the cumulative area X3.10.1.1 Find the pair of calibration compound retention
percent first equals or exceeds X. times that are closest to and bracket the percent off retention
NOTE X3.3—The cumulative area percent of a given slice is the sum of time of interest.
the normalized area percents from the start of sample slice through the X3.10.1.2 Calculate the boiling point corresponding to the
given slice. percent off retention time as follows:
X3.9.1.2 For the slice (N+1) determined above, the follow- BPi 5 ~~~BP2 – BP1! / ~RT2 – RT1!! 3 ~RTi – RT1!! 1 BP1
ing inequality should hold: (X3.4)
CAN ,5 X ,5 CAN11 (X3.1) where:
where: BPi = boiling point for i percent off,
CAN = the cumulative area percent from start of sample RTi = retention time for i percent off,
RT1 = retention time of calibration compound immediately
slice through slice N, and
CAN+1 = the cumulative area percent through slice N+1. preceding RTi,
RT2 = retention time of calibration compound immediately
X3.9.1.3 Calculate the fraction (f) of normalized area per-
following RTi,
cent in slice (N+1) needed to give exactly X percent off as BP1 = boiling point of compound at RT1, and
follows: BP2 = boiling point of compound at RT2.
f 5 ~X – CAN! / AN11 (X3.2)
NOTE X3.4—A report giving percent off at selected boiling point
where: intervals can be calculated in an analogous manner.
AN+1 = the normalized area percent (not cumulative) of
slice N+1. X3.11 Reporting Results
X3.9.1.4 The retention time corresponding to X percent off X3.11.1 Report the IBP, the temperatures corresponding to 1
(RTX) is the retention time of the fractional slice (N+f) and is to 99 % off, and the FBP to the nearest whole degree
calculated as follows: Fahrenheit or nearest half degree Celsius.
X4. CALCULATION OF D86 CORRELATED DATA FROM D2887 DATA
X4.1 Correlations TABLE X4.1 STP 577 Correlation

D86-IBP 46.566 + 0.58289 (D2887 10 %) + 0.34795 (D2887 IBP)
X4.1.1 The resulting data obtained from carrying out an D86-10 % 33.308 + 0.61562 (D2887 10 %) + 0.35110 (D2887 20 %)
analysis by Test Method D2887 can be used to obtain Test D86-20 % 22.411 + 0.48903 (D2887 30 %) + 0.27528 (D2887 20 %) +
Method D86 data via a correlation. The correlations used to 0.21713 (D2887 10 %)
D86-30 % 14.431 + 0.47035 (D2887 30 %) + 0.28369 (D2887 20 %) +
convert selected Test Method D2887 distillation points (per- 0.22784 (D2887 50 %)
cent off) to Test Method D86 (percent off) are mathematical D86-50 % 4.876 + 0.97597 (D2887 50 %)
equations. There are two correlations presented in this appen- D86-70 % 0.911 + 0.51975 (D2887 80 %) + 0.33260 (D2887 70 %) + 0.10159
(D2887 30 %)
dix: the STP 577 correlation and the API correlation. D86-80 % 0.279 + 0.75936 (D2887 80 %) + 0.28333 (D2887 95 %) − 0.09975
(D2887 FBP)
X4.2 STP 577 Correlation D86-90 % −1.973 + 0.61459 (D2887 90 %) + 0.31909 (D2887 95 %)
D86-FBP 34.179 + 1.14826 (D2887 95 %) − 0.59208 (D2887 90 %) +
X4.2.1 The correlation that has been used for a number of 0.31542 (D2887 FBP)
years is called the Atlantic Richfield correlation, which was

published in an ASTM Special Technical Publication (STP
statistical methodologies. However, a limited number of com-
577) (4). See Table X4.1.
parisons of the use of the correlation is presented in Reference
X4.2.2 The application of this correlation was also pub- (4).
lished by Kennard (5), which showed how the correlation can
be optimized for a particular type of sample. X4.3 API Correlation
X4.2.3 This correlation has not been subjected to recent X4.3.1 A second correlation that has been used is the API
ASTM statistical treatment since its origin precedes the newer Procedure 3A3.2 (see Reference (6)).
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13
D2887 – 08
X5. CORRELATION FOR JET AND DIESEL FUEL
X5.1 The resulting data obtained from carrying out an ai = ith coefficient from Table X5.1, and
analysis by Test Method D2887 can be used to obtain Test Tn = nth boiling point temperature of D2887.
Method D86 data via a correlation. The correlations used to
convert selected Test Method D2887 distillation points (per- X5.6 Basis
cent off) to Test Method D86 (percent off) are mathematical X5.6.1 This correlation model is based on data for 46 jet
equations. fuel samples and 39 diesel fuel samples analyzed in accordance
with both Test Method D86 and D2887. From these results, a
X5.2 A correlation model is presented here for the calcu- correlation model was determined using regression, specifying
lation of Test Method D86 correlated data from boiling range coefficients per recovery. A model of the remaining bias was
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distribution analysis by gas chromatography according to Test determined by use of Practice D6708 on a dataset from the
Method D2887. This correlation model is only valid for diesel ASTM Interlaboratory Crosscheck Program of five jet fuels
and jet fuels, excluding biodiesels. and six diesels analyzed by 38 laboratories by Test Method
X5.3 This correlation model was validated by an analysis D2887 and 201 laboratories by Test Method D86.
of variance procedure in accordance with Practice D6708. X5.6.2 The bias correction model was used to correct the
results from the correlation model, resulting in a new correla-
X5.4 Significance and Use tion matrix given in Table X5.1.
X5.4.1 Valid data for conversion to Test Method D86 X5.6.3 Based on statistical significance tests, no sample
correlated data can be obtained by Test Method D2887. The specific biases were observed in the dataset used for the bias
model is only valid for diesel or jet fuel and samples must meet correction.
the specifications given in Test Method D2887. X5.6.4 Both methods were found sufficiently precise to
distinguish among the samples.
X5.5 Summary of the Procedure X5.6.5 Precision and Bias8—Reproducibility after conver-
X5.5.1 Test Method D86 correlated data is calculated from sion of Test Method D2887 data into Test Method D86 data is
Test Method D2887 data using Eq X5.1 and the coefficients equivalent to the reproducibility of Test Method D2887.
specified in Table X5.1. X5.6.6 Cross-method reproducibility after conversion of
tn 5 ao 1 a1 · Tn21 1 a2 · Tn 1 a3 · Tn11 (X5.1) Test Method D2887 data into Test Method D86 correlated data
is given in Table X5.2.
where:
tn = nth boiling point temperature of Test Method D86 8
Supporting data have been filed at ASTM International Headquarters, and may
correlated,
be obtained by requesting Research Reports RR:D02-1553 and D02–1564.
TABLE X5.1 Correlation Coefficients

tn°C a0 a1 a2 a3 Tn-1 Tn°C Tn+1
IBP 25.351 0.32216 0.71187 -0.04221 TIBP T5 T10
5% 18.822 0.06602 0.15803 0.77898 TIBP T5 T10
10 % 15.173 0.20149 0.30606 0.48227 T5 T10 T20
20 % 13.141 0.22677 0.29042 0.46023 T10 T20 T30
30 % 5.7766 0.37218 0.30313 0.31118 T20 T30 T50
50 % 6.3753 0.07763 0.68984 0.18302 T30 T50 T70
70 % -2.8437 0.16366 0.42102 0.38252 T50 T70 T80
80 % -0.21536 0.25614 0.40925 0.27995 T70 T80 T90
90 % 0.09966 0.24335 0.32051 0.37357 T80 T90 T95
95 % 0.89880 -0.09790 1.03816 -0.00894 T90 T95 TFBP
FBP 19.444 -0.38161 1.08571 0.17729 T90 T95 TFBP
TABLE X5.2 Cross-Method Reproducibility, °C

IBP 5% 10 % 20 % 30 % 50 % 70 % 80 % 90 % 95 % FBP
R°C 13.71 11.80 10.73 8.83 7.39 6.96 7.03 7.62 8.85 17.32 12.94

14
D2887 – 08
X6. ACCELERATED TEST METHOD D2887
X6.1 This section has been added to the test method to TABLE X6.1 Typical Operating Parameters for Accelerated Test
provide guidance for carrying out Test Method D2887 in an Method D2887
accelerated mode. Without instrumental adaptation, it is pos- Column 1 Column 2
sible to significantly reduce analysis times. The term acceler- Column length (m) 10 5
ated is used here to distinguish this technique from fast Column ID (mm) 0.53 0.53
Stationary phase thickness (µm)A 0.88 2.65
chromatography, which requires direct heating of the column Carrier gas helium helium
only. Carrier gas flow rate (mL/min) 26 35
Initial column temperature (°C) 40 40
X6.2 The development of gas chromatographic ovens, Final column temperature (°C) 360 350
Oven programming rate (°C/min) 35 35
which allow reproducible heating rates from 10 to 35ºC°C/min, Detector FID FID
allows the chromatography to be carried out in shorter periods Detector temperature (°C) 360 360
of time, by decreasing the run time from about 20 min to 8 to Injector cold on-column cold on-column
Injector initial temperature (°C) 100 100
9 min. Two sets of typical operating conditions are provided in Injector programming rate (°C/min) 35 35
Table X6.1. Injector final temperature (°C) 360 350
Sample size (µL) 0.1 0.1
X6.3 Figs. X6.1 and X6.2 show chromatograms of the Dilution concentration neat neat
Analysis time (minutes) 8 7.8
retention time standard analyzed at an oven-heating rate of A
All columns contain a polydimethylsiloxane stationary phase.
35ºC/min with Columns 2 and 1, respectively.
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X6.4 Figs. X6.3 and X6.4 show chromatograms of the

reference gas oil eluting in about 8 min for Columns 2 and 1, tions with the results listed in Test Method D2887 as shown in
respectively. the column labeled Delta which tabulates the difference. From
the average of the duplicate runs, the repeatability standard
X6.5 Table X6.2 shows the results obtained by analyzing deviation is given in Table X6.2. This temporary repeatability
the reference gas oil in three different instruments by injecting standard deviation is determined so as to comply with Section
the reference gas oil in duplicate by three different operators A.21.2.3 of the Form and Style Manual for ASTM Standards.
utilizing Column 2. Table X6.2 also shows the comparison of Final repeatability and reproducibility precision will be avail-
the reference gas oil values obtained under accelerated condi- able on or before 2010 by completing an interlaboratory study.

15
D2887 – 08
FIG. X6.1 Retention Time Standard (Column 2)
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16
D2887 – 08
FIG. X6.2 Retention Time Standard (Column 1)
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17
D2887 – 08
--```,``,`,,``,````,``,,,``,,,`,-`-`,,`,,`,`,,`---
FIG. X6.3 Analysis of the Reference Gas Oil Under Accelerated Conditions (Column 2)
FIG. X6.4 Analysis of the Reference Gas Oil Under Accelerated Conditions (Column 1)

18
D2887 – 08
TABLE X6.2 Boiling Point Distribution (°F) Results Obtained for the Reference Gas Oil (Batch 2) Using an Accelerated Mode (Column
2)
Repeatability Accepted Reference Gas Oil Values Delta Values
Std Deviation
% Off BP (°F) (°F) (°C) (°F) (°F)
IBP 236.3 1.5 0.8 240 –3.7
5 304.3 1.2 0.7 304 0.3
10 348.2 1.4 0.8 348 0.2
15 393.9 1.2 0.7 393 0.9
20 436.3 2.0 1.1 435 1.3
25 470.9 2.9 1.6 ... ...
30 500.3 2.3 1.3 499 1.3
35 527.7 2.3 1.3 ... ...
40 554.4 1.1 0.6 552 2.4
45 577.1 2.1 1.2 ... ...
50 595.3 2.0 1.1 594 1.3
55 611.4 2.8 1.6 ... ...
60 630.1 1.6 0.9 629 1.1
65 649.9 1.7 1.0 649 0.9
70 669.8 1.5 0.8 668 1.8
75 691.5 1.4 0.8 690 1.5
80 713.8 1.1 0.6 712 1.8
85 737.9 0.9 0.5 736 1.9
90 765.6 1.4 0.8 764 1.6
95 804.1 1.7 1.0 803 1.1
FBP 887.6 3.7 2.0 888 –0.4
X7. PREVIOUS CHANGES
X7.1 Subcommittee D02.04 has identified the location of (2) Corrected Footnote A in Table 2.
selected changes to this standard since the last issue (3) Removed Column Resolution requirement.
(D2887–01a) that may impact the use of this standard. (4) Added Appendix X3, Calculation Algorithm.
X7.1.1 Changes: (5) Corrected rate of change of chromatographic signal in
(1) Corrected selected Fahrenheit boiling point values in Note 8.
Table 2 and added a note explaining the derivation of the (6) Modified paragraph 6.1.5 to address inlet pressure for
corrected values. open tubular columns.
REFERENCES
(1) Green, L. E., Schumauch, L. J., and Worman, J. C., Analytical Properties of Petroleum Products From Gas Chromatographic Analy-
Chemistry., Vol 32, 1960, p. 904. ses,” Ed. by L. E. Green and D. K. Albert, ASTM STP 577, ASTM
(2) Hickerson, J. F., ASTM STP 577M, ASTM International, 1973, p. 71. International, 1975, pp. 20-30.
(3) Green, L. E., Chromatograph Gives Boiling Point, Hydrocarbon (5) Kennard, C., “Correlated ASTM Distillation Distribution Based on
Processing, May, 1976. Simulated Distillation (ASTM D2887) Data,” Hewlett Packard, Avon-
(4) Ford, D. C., Miller, W. H., Thren, R. C., and Wetzler, R., “Correlation dale, PA, Application Note AN230-5, April 1979.
of ASTM D2887-73 Boiling Range Distribution Data with ASTM (6) API Technical Data Book for Petroleum Refining, Chapter 3, Petro-
Method D86-67D86 Distillation Data” In “Calculation of Physical leum Fraction Distillation Interconversions, 1999.
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19
D2887 – 08
SUMMARY OF CHANGES
Subcommittee D02.04.0H has identified the location of selected changes to this standard since the last issue
(D2887–06a) that may impact the use of this standard.
(1) Added Note 1. (3) Revised 10.3.

(2) Replaced 55°C with 55.5°C in 1.1. (4) Revised 10.4.1.
ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.
This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.
This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
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COPYRIGHT/).
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What is the purpose of this test method?

What is the purpose of this test method?

What are some of the terms defined in this test method?

What are some of the terms defined in this test method?

Designation: D2887 – 08

Standard Test Method for

1. Scope* D86 Test Method for Distillation of Petroleum Products at

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

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6.1.6 Microsyringe—A microsyringe is needed for sample 7. Reagents and Materials

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9.2.1.6 Hold the column at this temperature for at least 1 h

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FIG. 2 Typical Calibration Curve

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X1. BOILING POINTS OF NONPARAFFINIC HYDROCARBONS

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TABLE X1.1 Compound Identification—Numbered Dots (see Fig. X1.1)

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TABLE X1.3 Distillation of Heavy Gas Oils

X2. AGREEMENT WITH CONVENTIONAL DISTILLATION

Method D2892 on the same samples by a number of labora-

X3. CALCULATION ALGORITHM

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X4. CALCULATION OF D86 CORRELATED DATA FROM D2887 DATA

X4.1 Correlations TABLE X4.1 STP 577 Correlation

years is called the Atlantic Richfield correlation, which was

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X5. CORRELATION FOR JET AND DIESEL FUEL

TABLE X5.1 Correlation Coefficients

TABLE X5.2 Cross-Method Reproducibility, °C

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X6. ACCELERATED TEST METHOD D2887

X6.4 Figs. X6.3 and X6.4 show chromatograms of the

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FIG. X6.1 Retention Time Standard (Column 2)

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FIG. X6.2 Retention Time Standard (Column 1)

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X7. PREVIOUS CHANGES

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(1) Added Note 1. (3) Revised 10.3.

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