ASTM D2789-95(2016)

Standard Test Method for Hydrocarbon Types in Low Olefinic Gasoline by Mass Spectrometry (Withdrawn 2023)

SIGNIFICANCE AND USE
5.1 A knowledge of the hydrocarbon composition of gasoline process streams, blending stocks and finished motor fuels is useful in following the effect of changes in plant operating conditions, diagnosing process upsets, blending finished products and in evaluating the relationship between composition and performance properties.
SCOPE
1.1 This test method covers the determination by mass spectrometry of the total paraffins, monocycloparaffins, dicycloparaffins, alkylbenzenes, indans or tetralins or both, and naphthalenes in gasoline having an olefin content of less than 3 % by volume and a 95 % distillation point of less than 210 °C (411 °F) as determined in accordance with Test Method D86. Olefins are determined by Test Method D1319, or by Test Method D875.  
1.2 It has not been determined whether this test method is applicable to gasoline containing oxygenated compounds (for example, alcohols and ethers).  
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
WITHDRAWN RATIONALE
This test method covered the determination by mass spectrometry of the total paraffins, monocycloparaffins, dicycloparaffins, alkylbenzenes, indans or tetralins or both, and naphthalenes in gasoline having an olefin content of less than 3 % by volume and a 95 % distillation point of less than 210 °C (411 °F) as determined in accordance with Test Method D86.
Formerly under the jurisdiction of Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants, this test method was withdrawn without replacement in March 2023. This test method was created in 1969 and had a precision statement but no referenced research report. ASTM archives do not have a research report on file; Form and Style Guide requires a research report. The test method was originally developed for specific types of magnetic sector mass spectrometers and published calculations were based on such instrumentation. As a result, there was no easy mechanism to update the test method without method development. In addition, the committee understands that this method may not be performed by many, if any, laboratories. There are several test methods (e.g. D5443), although not fully equivalent to D2789, that provide compositional data for such low olefinic streams. ASTM will continue to provide copies of the test method for those that may need it. Committee D02.04M encourages members to submit potential replacement test method(s), based on newer technologies that can be developed into ASTM approved test method(s).

General Information

• Status: Withdrawn
• Publication Date: 30-Sep-2016
• Withdrawal Date: 06-Mar-2023
• ICS: 75.160.20 - Liquid fuels
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.04.0M - Mass Spectrometry

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D2789 − 95 (Reapproved 2016)
Standard Test Method for
Hydrocarbon Types in Low Olefinic Gasoline by Mass
Spectrometry
This standard is issued under the fixed designation D2789; 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 D2001 Test Method for Depentanization of Gasoline and
Naphthas
1.1 This test method covers the determination by mass
D2002 Practice for Isolation of Representative Saturates
spectrometry of the total paraffins, monocycloparaffins,
Fraction from Low-Olefinic Petroleum Naphthas (With-
dicycloparaffins, alkylbenzenes, indans or tetralins or both, and
drawn 1998)
naphthalenes in gasoline having an olefin content of less than
3 % by volume and a 95 % distillation point of less than 210 °C
3. Terminology
(411 °F) as determined in accordance with Test Method D86.
3.1 Definitions of Terms Specific to This Standard:
Olefins are determined by Test Method D1319, or by Test
3.1.1 The summations of characteristic mass fragments are
Method D875.
defined as follows (equations are identical to those in 11.1):
1.2 It has not been determined whether this test method is
applicable to gasoline containing oxygenated compounds (for
43 ~paraffins! 5 total peak height of m/e 43157171185199.
(
example, alcohols and ethers).
(1)
1.3 The values stated in SI units are to be regarded as 1
41 monocycloparaffins 5 total peak height of m/e 41155169183
~ !
(
standard. No other units of measurement are included in this
197. (2)
standard.
67 dicycloparaffins 5 total peak height of m/e 67168181182
~ !
(
1.4 This standard does not purport to address all of the
195196. (3)
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
77 alkylbenzenes 5 total peak height of m/e 77178179191192
~ !
(
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use.
11611162. (4)
2. Referenced Documents
103 indans and tetralins 5 total peak height of m/e 10311041117
~ !
(
2.1 ASTM Standards:
1118113111321145114611591160.
D86 Test Method for Distillation of Petroleum Products and
(5)
Liquid Fuels at Atmospheric Pressure
128 naphthalenes 5 total peak height of m/e 128114161421155
~ !
(
D875 Method for Calculating of Olefins and Aromatics in
1156. (6)
Petroleum Distillates from Bromine Number and Acid
Absorption (Withdrawn 1984)
T 5 total ion intensity5 411 431 671 771 1031 128.
( ( ( ( ( (
D1319 Test Method for Hydrocarbon Types in Liquid Petro-
(7)
leum Products by Fluorescent Indicator Adsorption
3.1.2 carbon number—by definition, is the average number
of carbon atoms in the sample.
This test method is under the jurisdiction of ASTM Committee D02 on
3.1.3 mass number—with a plus sign as superscript, is
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
defined as the peak height associated with the same mass
Subcommittee D02.04.0M on Mass Spectroscopy.
number.
Current edition approved Oct. 1, 2016. Published November 2016. Originally
approved in 1969. Last previous edition approved in 2011 as D2789 – 95 (2011).
DOI: 10.1520/D2789-05R16.
4. Summary of Test Method
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
4.1 Samples are analyzed by mass spectrometry, based on
Standards volume information, refer to the standard’s Document Summary page on
the summation of characteristic mass fragments, to determine
the ASTM website.
3 the concentration of the hydrocarbon types. The average
The last approved version of this historical standard is referenced on
www.astm.org. number of carbon atoms of the sample is estimated from
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D2789 − 95 (2016)
should develop their own calibration data using the blends described in
spectral data. Calculations are made from calibration data
Table 2.
which are dependent upon the average number of carbon atoms
of the sample. Results are expressed in liquid volume percent. 6.2 Sample Inlet System—Any sample inlet system that
allows the introduction of the text mixture (8.2) without loss,
5. Significance and Use
contamination, or change of composition.
5.1 A knowledge of the hydrocarbon composition of gaso-
NOTE 2—Laboratory testing has shown that, unless a special sampling
line process streams, blending stocks and finished motor fuels
technique or a heated inlet system is used, relatively large errors will occur
is useful in following the effect of changes in plant operating
in the determination of small quantities of indans, tetralins, and naphtha-
lenes.
conditions, diagnosing process upsets, blending finished prod-
ucts and in evaluating the relationship between composition
6.3 Manometer—A manometer suitable for direct reading in
and performance properties.
the 0 mtorr to 100 mtorr (0 Pa to 13 Pa) range is optional.
6. Apparatus NOTE 3—The expression mtorr as used in this procedure replaces the
older µ (micron) unit of pressure.
6.1 Mass Spectrometer—Any mass spectrometer that passes
6.4 Microburet or Constant-Volume Pipet.
the performance test described in Section 8.
NOTE 1—Calibration and precision data for this method were obtained
7. Reference Standards
on Consolidated Electrodynamics Corp. Type 21-101, 21-102, and 21-103
mass spectrometers. These instruments operated with an ion source
7.1 Samples of the following hydrocarbons will be required:
temperature at or near 250 °C and at a constant magnetic field of about
2-methylpentane, 2,4-dimethylpentane, n-octane,
3100 gauss (G) to 3500 G. Laboratories using either Consolidated Elec-
methylcyclopentane, methylcyclohexane, cis-1,2-
trodynamics Corp. mass spectrometers that operate with different param-
dimethylcyclohexane, benzene, toluene, and p-xylene
eters or instruments other than this design should check the applicability
of the calibration data in Table 1. If necessary, individual laboratories (Warning—Extremely flammable liquids. Benzene is a
TABLE 1 Calibration Data
A
^43/T ^41/T ^67/T ^77/T ^103/T ^128/T Reference
Paraffins:
C 0.6949 0.3025 0.0019 0.0006 . . (1)
C 0.7379 0.2583 0.0027 0.0010 . . (3)
C 0.7592 0.2362 0.0032 0.0014 . . (3)
C 0.7462 0.2350 0.0052 0.0021 . 0.0113 (12)
C 0.7772 0.2007 0.0056 0.0014 . 0.0151 (13)
Monocycloparaffins:
C 0.1234 0.8218 0.0460 0.0086 . . (1)
C 0.0731 0.8213 0.0952 0.0104 . . (3)
C 0.0737 0.8279 0.0866 0.0117 . . (3)
C 0.0884 0.8029 0.0942 0.0140 0.0003 0.0003 (12)
C 0.1471 0.6272 0.2176 0.0080 . . (13)
Dicycloparaffins:
C 0.0057 0.1848 0.7843 0.0246 0.0004 . (4)
C 0.0171 0.2270 0.7070 0.0483 0.0005 . (5)
C 0.0114 0.2973 0.6582 0.0324 0.0006 . (6)
Alkylbenzenes:
C 0.0004 0.0004 . 0.9992 . . (2)
C 0.0146 0.0120 0.0007 0.9726 . . (3)
C 0.0033 0.0112 0.0007 0.9488 0.0359 . (3)
C 0.0061 0.0218 0.0020 0.9103 0.0598 . (12)
C 0.0095 0.0350 0.0025 0.8656 0.0839 0.0034 (13)
Indans and tetralins:
C 0.0144 0.0101 0.0002 0.1600 0.8154 . (7)
C 0.0062 0.0123 0.0044 0.2314 0.7236 0.0222 (8)
C 0.0231 0.0199 0.0017 0.1619 0.7456 0.0477 (9)
Naphthalenes:
C 0.0121 0.0037 0.0008 0.0581 0.0065 0.9188 (10)
C 0.0702 0.0140 0.0011 0.0172 0.0018 0.8957 (11)
A
References to source of calibration data:
(1) National cooperative by letter of Nov. 22, 1965.
(2) Local task group cooperative by meeting of March 1966.
(3) National cooperative by letter of Aug. 6, 1962.
(4) API No. 448, 100 %, bicyclo-(3.3.0)-octane.
(5) Shell data, 100 %, for 1-methyl-cis-(3.3.0)-bicyclooctane.
(6) API No. 412, 100 %, trans-decalin.
(7) Unweighted API No. 413 and No. 1214 spectra of indan.
(8) API No. 1103, 13 %; API No. 1104, 13 %; API No. 941, 37 %; API No. 539, 37 %.
(9) Unweighted averages of API Nos. 1216, 1106, 1107, 1108, 1109.
(10) Unweighted average of local task group (3 laboratories) data.
(11) Unweighted average of API No. 990 and No. 991.
(12) National cooperative by letter of Oct. 11, 1967.
(13) Proposed Method of Test for Hydrocarbon Types in Low Olefinic Gasoline by Mass Spectrometry; Appendix VII D2-1958.
D2789 − 95 (2016)
TABLE 2 Compositions of Calibration Mixtures
Cyclo-Alkyl- Cyclo- Alkyl-
Component (Volume Percent) Paraffins Cyclo-paraffins Component (Volume Percent) Paraffins
benzenes paraffins benzenes
C Blends C Blends
6 9
n-Hexane 46 . . n-Nonane 33 . .
2-Methylpentane 28 . . 2-Methyloctane 20 . .
3-Methylpentane 20 . . 3-Methyloctane 16 . .
2-2-Dimethylbutane 1 . . 4-Methyloctane 8 . .
2,3-Dimethylbutane 5 . . 3-Ethylheptane 3 . .
Cyclohexane . 46 . 2,6-Dimethylheptane 12 . .
Methylcyclopentane . 54 . 2,2-Dimethylheptane 2 . .
Benzene . . 100 3,3-Diethylpentane 1 . .
2,2,5-Trimethylhexane 2 . .
C Blends
2,2,5-Trimethylhexane 1 . .
n-Heptane 45 . . 2,4-Dimethyl-3-ethylpentane 1 . .
2-Methylhexane 23 . . 2,2,3,3-Tetramethylpentane 1 . .
3-Methylhexane 16 . . n-Propylcyclohexane . 1 .
2,2-Dimethylpentane 4 . . Isopropylcyclohexane . 2 .
2,3-Dimethylpentane 6 . . 1-Methyl-c-2-ethylcyclohexane . 3 .
2,4-Dimethylpentane 5 . . 1-Methyl-t-2-ethylcyclohexane . 4 .
3,3-Dimethylpentane 1 . . 1-Methyl-c-3-ethylcyclohexane . 8 .
Methylcyclohexane . 57 . 1-Methyl-t-3-ethylcyclohexane . 8 .
Ethylcyclopentane . 9 . 1-Methyl-c-4-ethylcyclohexane . 4 .
1,1-Dimethylcyclopentane . 4 . 1-Methyl-t-4-ethylcyclohexane . 5 .
1,t-2-Dimethylcyclopentane . 14 . 1,c-2, c-3-trimethylcyclohexane . 2 .
1,t-3-Dimethylcyclopentane . 16 . 1,t-2, t-3-trimethylcyclohexane . 3 .
Toluene . . 100 1,t-2,c-3-trimethylcyclohexane . 3 .
1,t-2,c-4-trimethylcyclohexane . 15 .
C Blends
1,t-2,t-4-trimethylcyclohexane . 15 .
n-Octane 39 . . 1,c-3,c-5-trimethylcyclohexane . 5 .
2-Methylheptane 19 . . 1,c-3,t-5-trimethylcyclohexane . 5 .
3-Methylheptane 16 . . n-Butylcyclopentane . 1 .
4-Methylheptane 8 . . 1,c-2-Diethylcyclopentane . 12 .
3-Ethylhexane 3 . . 1,t-2,c-3,t-4-tetramethylcyclopentane . 4 .
2,3-Dimethylhexane 4 . . n-Propylbenzene . . 3
2,4-Dimethylhexane 5 . . Isopropylbenzene . . 1
2,5-Dimethylhexane 6 . . 1-Methyl-2-ethylbenzene . . 8
Ethylcyclohexane . 20 . 1-Methyl-3-ethylbenzene . . 19
1,t-2-Dimethylcyclohexane . 18 . 1-Methyl-4-ethylbenzene . . 11
1,c-3-Dimethylcyclohexane . 25 . 1,2,3-Trimethylbenzene . . 10
1,t-4-Dimethylcyclohexane . 11 . 1,2,4-Trimethylbenzene . . 36
1-Methyl-c-2-ethylcyclopentane . 7 . 1,3,5-Trimethylbenzene . . 12
1,1,3-Trimethylcyclopentane . 5 .
1,t-2,c-3-Trimethylcyclopentane . 9 .
1,t-2,c-4-Trimethylcyclopentane . 5 .
Ethylbenzene . . 10
p-Xylene . . 23
m-Xylene . . 46
o-Xylene . . 21
poison, carcinogen, and is harmful or fatal if swallowed.). Only 8. Performance Test
reagent grade chemicals conforming to the specifications of the
8.1 Calibration for Test Mixture—Calibrate the instrument
Committee on Analytical Reagents of the American Chemical
in accordance with the manufacturer’s instructions for the
Society, National Institute of Standards and Technology
compounds listed in 7.1, using the same manipulative tech-
(NIST) standard hydrocarbon samples, or other hydrocarbons
nique as described in 10.2. Express the calibration data in units
of equal purity should be used.
of peak height per unit of liquid volume (V) at constant
sensitivity. Determine ∑41/V, ∑43/ V, and ∑77/V for each of
the reference standards and calculate a weighted average value
Reagent Chemicals, American Chemical Society Specifications, American
for each hydrocarbon group type in accordance with the
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
composition of the test mixture as described in 8.2. Construct
listed by the American Chemical Society, see Annual Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
an inverse from the averaged coefficients.
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD. NOTE 4—The volume, V, ordinarily is expressed as microlitres.
D2789 − 95 (2016)
NOTE 5—A desk calculator frequently is used for the calculation of 8.1
the inlet system to give a pressure of 20 to 60 mtorr (2.7 to 8.0
and in such cases small inverse terms can be undesirable. If necessary, it
Pa). Record the amount of sample introduced and the final
is permissible to divide all averaged coefficients by some suitable constant
pressure after expansion into the inlet system when a microbu-
prior to inversion in order to obtain larger values in the inverse.
ret and manometer are used. Recharge the sample until
8.2 Test Mixture—Prepare the synthetic mixture by weight
pressure readings that differ by 1 % or less are obtained.
from reference standards to obtain a final composition ap-
Attaining this pressure check means that a given microburet is
proximating the following but accurately known within 6
being used at constant volume. When the pressure check is
0.07 %:
obtained, admit the sample to the mass spectrometer and record
Approximate +
the mass spectrum of the sample from m/e 32 to 186.
Liquid
Weight
Volume
Reference Standard in Grams
Percent in
to Give
11. Calculation
Mixture
5 mL of Mixture
2-Methylpentane 7.2 0.237
11.1 Peaks—Read peak heights from the record of the mass
2,4-Dimethylpentane 9.4 0.318
+
spectrum of the sample corresponding to m/e ratios of 41, 43,
n-Octane 16.6 0.587
Methylcyclopentane 7.1 0.267 55, 57, 67, 68, 69, 71, 77, 78, 79, 81, 82, 83, 84, 85, 86, 91, 92,
Methylcyclohexane 10.0 0.387
95, 96, 97, 98, 99, 100, 103, 104, 105, 106, 112, 113, 114, 117,
cis-1,2-Dimethylcyclohexane 15.5 0.620
118, 119, 120, 126, 127, 128, 131, 132, 133, 134, 140, 141,
Benzene 7.7 0.341
Toluene 10.0 0.436
142, 145, 146, 147, 148, 154, 155, 156, 159, 160, 161, 162,
p-Xylene 16.5 0.714
168, 169, 170.
100.0 3.907
+
11.1.1 Calculate the following combined peak heights by
Record the mass spectrum of the test mixture from m/e 32
adding together the indicated peaks:
to 120 using the manipulative technique as described in 10.2.
Compute
...