ASTM D3239-91(1996)

Standard Test Method for Aromatic Types Analysis of Gas-Oil Aromatic Fractions by High Ionizing Voltage Mass Spectrometry

SCOPE
1.1 This test method covers the determination by high ionizing voltage, low resolution mass spectrometry of 18 aromatic hydrocarbon types and 3 aromatic thiophenotypes in straight run aromatic petroleum fractions boiling within the range from 205 to 540°C (400 to 1000°F) (corrected to atmospheric pressure). Samples must be nonolefinic, must contain not more than 1 mass % of total sulfur, and must contain not more than 5 % nonaromatic hydrocarbons. Composition data are in volume percent.
Note 1—Although names are given to 15 of the compound types determined, the presence of other compound types of the same empirical formulae is not excluded. All other compound types in the sample, unidentified by name or empirical formula, are lumped into six groups in accordance with their respective homologous series.
1.2 The values stated in acceptable SI units are to be regarded as the standard. The values given in parentheses are provided for information purposes only.
1.3 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.

General Information

• Status: Historical
• Publication Date: 14-Oct-1991
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.04.0M - Mass Spectrometry

Relations

• Replaced By: ASTM D3239-91(2001) - Standard Test Method for Aromatic Types Analysis of Gas-Oil Aromatic Fractions by High Ionizing Voltage Mass Spectrometry
• Effective Date: 15-Oct-1991

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NOTICE: This standard has either been superseded and replaced by a new version or
withdrawn.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: D 3239 – 91 (Reapproved 1996) An American National Standard
AMERICAN SOCIETY FOR TESTING AND MATERIALS
100 Barr Harbor Dr., West Conshohocken, PA 19428
Reprinted from the Annual Book of ASTM Standards. Copyright ASTM
Standard Test Method for
Aromatic Types Analysis of Gas-Oil Aromatic Fractions by
High Ionizing Voltage Mass Spectrometry
This standard is issued under the fixed designation D 3239; 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 (e) indicates an editorial change since the last revision or reapproval.
1. Scope 3. Terminology
1.1 This test method covers the determination by high 3.1 Definitions of Terms Specific to This Standard:
ionizing voltage, low resolution mass spectrometry of 18 3.1.1 Characteristic Mass Summations— Classes I–VII:
aromatic hydrocarbon types and 3 aromatic thiophenotypes in 3.1.2 Class I:
straight run aromatic petroleum fractions boiling within the
(78 5 78 1 92 1 106 1 120 1 .to end, polyisotopic
range from 205 to 540°C (400 to 1000°F) (corrected to
1 91 1 105 1 119 1 .to end, monoisotopic (1)
atmospheric pressure). Samples must be nonolefinic, must
3.1.3 Class II:
contain not more than 1 mass % of total sulfur, and must
(104 5 104 1 118 1 132 1 146 1 .to end, polyisotopic
contain not more than 5 % nonaromatic hydrocarbons. Com-
1 117 1 131 1 145 1 .to end, monoisotopic (2)
position data are in volume percent.
3.1.4 Class III:
NOTE 1—Although names are given to 15 of the compound types
(129 5 130 1 144 1 158 1 172 1 .to end, polyisotopic
determined, the presence of other compound types of the same empirical
1 129 1 143 1 157 1 171 1 .to end, monoisotopic (3)
formulae is not excluded. All other compound types in the sample,
unidentified by name or empirical formula, are lumped into six groups in
3.1.5 Class IV:
accordance with their respective homologous series.
(128 5 128 1 142 1 156 1 170 1 .to end, polyisotopic
1.2 This standard does not purport to address all of the
1 141 1 155 1 169 1 .to end, monoisotopic (4)
safety concerns, if any, associated with its use. It is the
3.1.6 Class V:
responsibility of the user of this standard to establish appro-
(154 5 154 1 168 1 182 1 196 1 .to end, polyisotopic
priate safety and health practices and determine the applica-
1 167 1 181 1 195 1 .to end, monoisotopic (5)
bility of regulatory limitations prior to use.
3.1.7 Class VI:
1.3 The values stated in acceptable SI units are to be
regarded as the standard. The values given in parentheses are
(166 5 166 1 180 1 194 1 208 1 .to end, polyisotopic
provided for information purposes only.
1 179 1 193 1 207 1 .to end, monoisotopic (6)
3.1.8 Class VII:
2. Referenced Documents
(178 5 178 1 192 1 206 1 220 1 .to end, polyisotopic
2.1 ASTM Standards:
1 191 1 205 1 219 1 .to end, monoisotopic (7)
D 2549 Test Method for Separation of Representative Aro-
3.1.9 Classes, Compound Types, Empirical Formulae— See
matics and Nonaromatics Fractions of High-Boiling Oils
Table 1.
by Elution Chromatography
D 2786 Test Method for Hydrocarbon Types Analysis of
4. Summary of Test Method
Gas-Oil Saturate Fractions by High Ionizing Voltage Mass
4.1 The relative abundance of seven classes (I–VII) of
Spectrometry
aromatics in petroleum aromatic fractions is determined by
E 137 Practice for Evaluation of Mass Spectrometers for
mass spectrometry using a summation of peaks most charac-
Quantitative Analysis from a Batch Inlet
teristic of each class. Calculations are carried out by the use of
a 7 by 7 inverted matrix derived from published spectra of pure
This test method is under the jurisdiction of ASTM Committee D-2 on aromatic compounds. Each summation of peaks includes the
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
polyisotopic homologous series that contains molecular ions
D02.04 on Hydrocarbon Analysis.
and the monoisotopic homologous series one mass unit less
Current edition approved Oct. 15, 1991. Published December 1991. Originally
than the molecular ion series. Using characteristic summations
published as D 3239 – 73 T. Last previous edition D 3239 – 86.
Robinson, C. J., and Cook, G. L., Analytical Chemistry (ANCHA), Vol 41,
found in the monoisotopic molecular ion—1 series of peaks,
1969, p. 1548.
each class is further resolved to provide relative abundances of
Annual Book of ASTM Standards, Vol 05.01.
4 three compound types: nominal (Type 0), first overlap (Type
Annual Book of ASTM Standards, Vol 05.02.
1), and second overlap (Type 2). The aromatic fraction is
Discontinued—See 1992 Annual Book of ASTM Standards, Vol 05.03.
D 3239
TABLE 1 Classes, Compound Types, and Empirical Formulae
6.2 Sample Inlet System—Any inlet system may be used
Class Type Formula that permits the introduction of the sample without loss,
contamination, or change in composition. The system must
I 0 alkylbenzenes, C H
n 2n-6
I 1 benzothiophenes, C H S
n 2n-10 function in the range from 125 to 350°C to provide an
I 2 naphthenephenanthrenes,
appropriate sampling device.
C H
n 2n-20
6.3 Microburet or Constant-Volume Pipet.
II 0 naphthenebenzenes, C H
n 2n-8
II 1 pyrenes, C H
n 2n-22 6.4 Mass Spectrum Digitizer—It is recommended that a
II 2 unidentified
mass spectrum digitizer be used in obtaining the analysis,
III 0 dinaphthenebenzenes, C H
n 2n-10
because it is necessary to use the heights of most of the peaks
III 1 chrysenes, C H
n 2n-24
III 2 unidentified
in the spectrum. Any digitizing system capable of supplying
IV 0 naphthalenes, C H
n 2n-12
accurate mass numbers and peak heights is suitable.
IV 1 dibenzothiophenes, C H S
n 2n-16
6.5 Electronic Digital Computer—The computations for
IV 2 unidentified
V 0 acenaphthenes + dibenzofurans,
this analysis are not practical without the use of a computer.
C H and C H O
n 2n-14 n 2n-16
Any computer capable of providing approximately 60 K bytes
V 1 perylenes, C H
n 2n-28
in core and capable of compiling programs written in FOR-
V 2 unidentified
VI 0 fluorenes, C H
n 2n-16
TRAN IV should be suitable.
VI 1 dibenzanthracenes, C H
n 2n-30
VI 2 unidentified
7. Reagent
VII 0 phenanthrenes, C H
n 2n-18
7.1 n-Hexadecane
VII 1 naphthobenzothiophenes, C H
n 2n-
22S
NOTE 3—Warning: Combustible-Very harmful.
VII 2 unidentified
8. Calibration
obtained by liquid elution chromatography (see Test Method 8.1 Calibration equations in the computer program given in
Table 2 may be used directly provided the following proce-
D 2549).
dures are followed:
NOTE 2—Monoisotopic peaks heights are obtained by correcting the
8.1.1 Instrumental Conditions—Repeller settings are ad-
polyisotopic heights for naturally occurring heavy isotopes, assuming that
justed to maximize the m/e 226 ion of n-hexadecane. A
only ions of C H to C H are present. This is not strictly accurate
n 2n+2 n 2−11
magnetic field is used that will permit a scan over the mass
for aromatics, but the errors introduced by such assumption are trivial.
range from 78 to 700. An ionizing voltage of 70 eV and an
5. Significance and Use
ionizing current in the range from 10 to 70 μA is used.
5.1 A knowledge of the hydrocarbon composition of process
NOTE 4—The instrument conditions and calibration equations de-
streams and petroleum products boiling within the range 205 to
scribed in this method are based on the use of a 180° magnet
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