ASTM D3239-91(2006)
(Test Method)Standard Test Method for Aromatic Types Analysis of Gas-Oil Aromatic Fractions by High Ionizing Voltage Mass Spectrometry
Standard Test Method for Aromatic Types Analysis of Gas-Oil Aromatic Fractions by High Ionizing Voltage Mass Spectrometry
SIGNIFICANCE AND USE
A knowledge of the hydrocarbon composition of process streams and petroleum products boiling within the range 205 to 540°C (400 to 1000°F) is useful in following the effect of changes in process variables, diagnosing the source of plant upsets, and in evaluating the effect of changes in composition on product performance properties. This method, when used together with Test Method D 2786, provides a detailed analysis of the hydrocarbon composition of such materials.
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.
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.
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Designation:D3239–91(Reapproved 2006)
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 D3239; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope E137 Practice for Evaluation of Mass Spectrometers for
Quantitative Analysis from a Batch Inlet
1.1 This test method covers the determination by high
ionizing voltage, low resolution mass spectrometry of 18
3. Terminology
aromatic hydrocarbon types and 3 aromatic thiophenotypes in
3.1 Definitions of Terms Specific to This Standard:
straight run aromatic petroleum fractions boiling within the
3.1.1 Characteristic Mass Summations— Classes I–VII:
range from 205 to 540°C (400 to 1000°F) (corrected to
3.1.2 Class I:
atmospheric pressure). Samples must be nonolefinic, must
contain not more than 1 mass% of total sulfur, and must (78 578 192 1106 1120 1.toend,polyisotopic
191 1105 1119 1.toend,monoisotopic (1)
contain not more than 5% nonaromatic hydrocarbons. Com-
position data are in volume percent.
3.1.3 Class II:
(104 5104 1118 1132 1146 1.toend,polyisotopic
NOTE 1—Although names are given to 15 of the compound types
1117 1131 1145 1.toend,monoisotopic (2)
determined, the presence of other compound types of the same empirical
formulae is not excluded. All other compound types in the sample,
3.1.4 Class III:
unidentified by name or empirical formula, are lumped into six groups in
(129 5130 1144 1158 1172 1.toend,polyisotopic
accordance with their respective homologous series.
1129 1143 1157 1171 1.toend,monoisotopic (3)
1.2 The values stated in acceptable SI units are to be
3.1.5 Class IV:
regarded as the standard. The values given in parentheses are
provided for information purposes only. (128 5128 1142 1156 1170 1.toend,polyisotopic
1141 1155 1169 1.toend,monoisotopic (4)
1.3 This standard does not purport to address all of the
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 5154 1168 1182 1196 1.toend,polyisotopic
priate safety and health practices and determine the applica-
1167 1181 1195 1.toend,monoisotopic (5)
bility of regulatory limitations prior to use.
3.1.7 Class VI:
2. Referenced Documents
(166 5166 1180 1194 1208 1.toend,polyisotopic
1179 1193 1207 1.toend,monoisotopic (6)
2.1 ASTM Standards:
D2549 Test Method for Separation of Representative Aro-
3.1.8 Class VII:
matics and Nonaromatics Fractions of High-Boiling Oils
(178 5178 1192 1206 1220 1.toend,polyisotopic
by Elution Chromatography
1191 1205 1219 1.toend,monoisotopic (7)
D2786 Test Method for Hydrocarbon Types Analysis of
3.1.9 Classes, Compound Types, Empirical Formulae—See
Gas-Oil Saturates Fractions by High Ionizing Voltage
Table 1.
Mass Spectrometry
4. Summary of Test Method
This test method is under the jurisdiction of ASTM Committee D02 on 4.1 The relative abundance of seven classes (I–VII) of
PetroleumProductsandLubricantsandisthedirectresponsibilityofSubcommittee
aromatics in petroleum aromatic fractions is determined by
D02.04 on Hydrocarbon Analysis.
mass spectrometry using a summation of peaks most charac-
Current edition approved May 1, 2006. Published June 2006. Originally
teristic of each class. Calculations are carried out by the use of
approved in 1973. Last previous edition approved in 2001 as D3239–91 (2001).
DOI: 10.1520/D3239-91R06.
a7by7invertedmatrixderivedfrompublishedspectraofpure
Robinson, C. J., and Cook, G. L., Analytical Chemistry (ANCHA), Vol 41,
aromatic compounds. Each summation of peaks includes the
1969, p. 1548.
3 polyisotopic homologous series that contains molecular ions
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. Withdrawn.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D3239–91 (2006)
TABLE 1 Classes, Compound Types, and Empirical Formulae
in the spectrum. Any digitizing system capable of supplying
Class Type Formula accurate mass numbers and peak heights is suitable.
I 0 alkylbenzenes, C H
n 2n-6 6.5 Electronic Digital Computer—The computations for
I 1 benzothiophenes, C H S
n 2n-10
this analysis are not practical without the use of a computer.
I 2 naphthenephenanthrenes,
C H Any computer capable of providing approximately 60K bytes
n 2n-20
II 0 naphthenebenzenes, C H
n 2n-8
in core and capable of compiling programs written in FOR-
II 1 pyrenes, C H
n 2n-22
TRAN IV should be suitable.
II 2 unidentified
III 0 dinaphthenebenzenes, C H
n 2n-10
III 1 chrysenes, C H
n 2n-24
7. Reagent
III 2 unidentified
IV 0 naphthalenes, C H
n 2n-12
7.1 n-Hexadecane.(Warning—Combustible-Very harm-
IV 1 dibenzothiophenes, C H S
n 2n-16
ful.)
IV 2 unidentified
V 0 acenaphthenes + dibenzofurans,
C H and C H O
n 2n-14 n 2n-16
8. Calibration
V 1 perylenes, C H
n 2n-28
V 2 unidentified
8.1 Calibration equations in the computer program given in
VI 0 fluorenes, C H
n 2n-16
VI 1 dibenzanthracenes, C H
n 2n-30 Table 2 may be used directly provided the following proce-
VI 2 unidentified
dures are followed:
VII 0 phenanthrenes, C H
n 2n-18
VII 1 naphthobenzothiophenes, C H
n 2n- 8.1.1 Instrumental Conditions—Repeller settings are ad-
22S
justed to maximize the m/e 226 ion of n-hexadecane. A
VII 2 unidentified
magnetic field is used that will permit a scan over the mass
range from 78 to 700. An ionizing voltage of 70 eV and an
ionizing current in the range from 10 to 70 µA is used.
and the monoisotopic homologous series one mass unit less
NOTE 3—The instrument conditions and calibration equations de-
than the molecular ion series. Using characteristic summations
scribed in this method are based on the use of a 180° magnetic-deflection
found in the monoisotopic molecular ion—1 series of peaks,
type mass spectrometer (CEC Model 21-103). Satisfactory results have
eachclassisfurtherresolvedtoproviderelativeabundancesof
been obtained with some other magnetic deflection instruments. It is not
three compound types: nominal (Type 0), first overlap (Type
known if the equations are suitable for use on all other mass spectrometer
1), and second overlap (Type 2). The aromatic fraction is
types.
obtained by liquid elution chromatography (see Test Method
8.1.2 Computer Program—The FORTRAN program given
D2549).
in Table 2 contains all the equations for calculating the
NOTE 2—Monoisotopic peaks heights are obtained by correcting the
analysis, including those for calculating monoisotopic peak
polyisotopicheightsfornaturallyoccurringheavyisotopes,assumingthat
heights. The program is compiled and linked to create a
only ions of C H to C H are present. This is not strictly accurate
n 2n+2 n 2−11
for aromatics, but the errors introduced by such assumption are trivial.
computer load module that is available whenever needed.
When the spectrum shown inTable 3 is processed, thee results
5. Significance and Use
should agree with those shown in Table 4.
5.1 Aknowledgeofthehydrocarboncompositionofprocess
8.1.2.1 Data Input Format—The input format suggested in
streamsandpetroleumproductsboilingwithintherange205to
the main program may be changed to suit the needs of
540°C (400 to 1000°F) is useful in fo
...
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