1、Designation: D3239 91 (Reapproved 2016)Standard Test Method forAromatic Types Analysis of Gas-Oil Aromatic Fractions byHigh Ionizing Voltage Mass Spectrometry1This standard is issued under the fixed designation D3239; the number immediately following the designation indicates the year oforiginal ado
2、ption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method2covers the determination by highionizing voltage, low
3、resolution mass spectrometry of 18aromatic hydrocarbon types and 3 aromatic thiophenotypes instraight run aromatic petroleum fractions boiling within therange from 205 C to 540 C (400 F to 1000 F) (corrected toatmospheric pressure). Samples must be nonolefinic, mustcontain not more than 1 % by mass
4、of total sulfur, and mustcontain not more than 5 % nonaromatic hydrocarbons. Com-position data are in volume percent.NOTE 1Although names are given to 15 of the compound typesdetermined, the presence of other compound types of the same empiricalformulae is not excluded. All other compound types in t
5、he sample,unidentified by name or empirical formula, are lumped into six groups inaccordance with their respective homologous series.1.2 The values stated in acceptable SI units are to beregarded as the standard. The values given in parentheses areprovided for information purposes only.1.3 This stan
6、dard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 A
7、STM Standards:3D2549 Test Method for Separation of Representative Aro-matics and Nonaromatics Fractions of High-Boiling Oilsby Elution ChromatographyD2786 Test Method for Hydrocarbon Types Analysis ofGas-Oil Saturates Fractions by High Ionizing VoltageMass SpectrometryE137 Practice for Evaluation of
8、 Mass Spectrometers forQuantitative Analysis from a Batch Inlet (Withdrawn1992)43. Terminology3.1 Definitions of Terms Specific to This Standard:3.1.1 Characteristic Mass Summations Classes IVII:3.1.2 Class I:(78 5 78192110611201to end, polyisotopic (1)191110511191to end, monoisotopic3.1.3 Class II:
9、(104 5 1041118113211461to end, polyisotopic (2)1117113111451to end, monoisotopic3.1.4 Class III:(129 5 1301144115811721to end, polyisotopic (3)11291143115711711to end, monoisotopic3.1.5 Class IV:(128 5 1281142115611701to end, polyisotopic (4)1141115511691to end, monoisotopic3.1.6 Class V:(154 5 1541
10、168118211961to end, polyisotopic (5)1167118111951to end, monoisotopic3.1.7 Class VI:(166 5 1661180119412081to end, polyisotopic (6)1179119312071to end, monoisotopic3.1.8 Class VII:1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricantsand
11、is the direct responsibility ofSubcommittee D02.04.0M on Mass Spectroscopy.Current edition approved Oct. 1, 2016. Published November 2016. Originallyapproved in 1973. Last previous edition approved in 2011 as D3239 91 (2011).DOI: 10.1520/D3239-91R16.2Robinson, C. J., and Cook, G. L., Analytical Chem
12、istry (ANCHA), Vol 41,1969, p. 1548.3For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.4The last approved versio
13、n of this historical standard is referenced onwww.astm.org.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1(178 5 1781192120612201to end, polyisotopic (7)1191120512191to end, monoisotopic3.1.9 Classes, Compound Types, Empirical Formul
14、aeSeeTable 1.4. Summary of Test Method4.1 The relative abundance of seven classes (IVII) ofaromatics in petroleum aromatic fractions is determined bymass spectrometry using a summation of peaks most charac-teristic of each class. Calculations are carried out by the use ofa 7 by 7 inverted matrix der
15、ived from published spectra of purearomatic compounds. Each summation of peaks includes thepolyisotopic homologous series that contains molecular ionsand the monoisotopic homologous series one mass unit lessthan the molecular ion series. Using characteristic summationsfound in the monoisotopic molec
16、ular ion1 series of peaks,each class is further resolved to provide relative abundances ofthree compound types: nominal (Type 0), first overlap (Type1), and second overlap (Type 2). The aromatic fraction isobtained by liquid elution chromatography (see Test MethodD2549).NOTE 2Monoisotopic peaks heig
17、hts are obtained by correcting thepolyisotopic heights for naturally occurring heavy isotopes, assuming thatonly ions of CnH2n+2to CnH211are present. This is not strictly accuratefor aromatics, but the errors introduced by such assumption are trivial.5. Significance and Use5.1 Aknowledge of the hydr
18、ocarbon composition of processstreams and petroleum products boiling within the range205 C to 540 C (400 F to 1000 F) is useful in following theeffect of changes in process variables, diagnosing the source ofplant upsets, and in evaluating the effect of changes incomposition on product performance p
19、roperties. This method,when used together with Test Method D2786, provides adetailed analysis of the hydrocarbon composition of suchmaterials.6. Apparatus6.1 Mass SpectrometerThe suitability of the mass spec-trometer to be used with this method shall be proven byperformance tests described both here
20、in and in Practice E137.6.2 Sample Inlet SystemAny inlet system may be used thatpermits the introduction of the sample without loss,contamination, or change in composition. The system mustfunction in the range from 125 C to 350 C to provide anappropriate sampling device.6.3 Microburet or Constant-Vo
21、lume Pipet.6.4 Mass Spectrum DigitizerIt is recommended that amass spectrum digitizer be used in obtaining the analysis,because it is necessary to use the heights of most of the peaksin the spectrum. Any digitizing system capable of supplyingaccurate mass numbers and peak heights is suitable.6.5 Ele
22、ctronic Digital ComputerThe computations forthis analysis are not practical without the use of a computer.Any computer capable of providing approximately 60 K bytesin core and capable of compiling programs written in FOR-TRAN IV should be suitable.7. Reagent7.1 n-Hexadecane. (WarningCombustible-Very
23、 harm-ful.)8. Calibration8.1 Calibration equations in the computer program given inTable 2 may be used directly provided the following proce-dures are followed:8.1.1 Instrumental ConditionsRepeller settings are ad-justed to maximize the m/e 226 ion of n-hexadecane. Amagnetic field is used that will
24、permit a scan over the massrange from 78 to 700. An ionizing voltage of 70 eV and anionizing current in the range from 10 A to 70 A is used.NOTE 3The instrument conditions and calibration equations describedin this method are based on the use of a 180 magnetic-deflection typemass spectrometer (CEC M
25、odel 21-103). Satisfactory results have beenobtained with some other magnetic deflection instruments. It is not knownif the equations are suitable for use on all other mass spectrometer types.8.1.2 Computer ProgramThe FORTRAN program givenin Table 2 contains all the equations for calculating theanal
26、ysis, including those for calculating monoisotopic peakheights. The program is compiled and linked to create acomputer load module that is available whenever needed.When the spectrum shown in Table 3 is processed, thee resultsshould agree with those shown in Table 4.8.1.2.1 Data Input FormatThe inpu
27、t format suggested inthe main program may be changed to suit the needs ofindividual laboratories provided that true masses and peakheights are stored in the H(M) array.8.1.2.2 FORTRAN IV LanguageChanges in the programmay be required for compatibility with the particular comput-ing system to be used.
28、 These are permitted provided that thealtered program gives the results shown in Table 4 with theinput data of Table 3.TABLE 1 Classes, Compound Types, and Empirical FormulaeClass Type FormulaI 0 alkylbenzenes, CnH2n-6I 1 benzothiophenes, CnH2n-10SI 2 naphthenephenanthrenes,CnH2n-20II 0 naphtheneben
29、zenes, CnH2n-8II 1 pyrenes, CnH2n-22II 2 unidentifiedIII 0 dinaphthenebenzenes, CnH2n-10III 1 chrysenes, CnH2n-24III 2 unidentifiedIV 0 naphthalenes, CnH2n-12IV 1 dibenzothiophenes, CnH2n-16SIV 2 unidentifiedV 0 acenaphthenes + dibenzofurans,CnH2n-14and CnH2n-16OVV12perylenes, CnH2n-28unidentifiedVI
30、 0 fluorenes, CnH2n-16VI 1 dibenzanthracenes, CnH2n-30VI 2 unidentifiedVII 0 phenanthrenes, CnH2n-18VII 1 naphthobenzothiophenes, CnH2n-22SVII 2 unidentifiedD3239 91 (2016)2NOTE 4The program, as shown in Table 2, has run satisfactorily on IBM System 360 computers.TABLE 2 High Ionizing Voltage, Low R
31、esolution Mass Spectrometric Analysis of Gas Oil Aromatic Fractions* The “end statement” designated is specific for IBM computers. The user may modify the FORTRAN program to suit his individual needs.D3239 91 (2016)3TABLE 2 ContinuedD3239 91 (2016)4TABLE 2 ContinuedD3239 91 (2016)5TABLE 2 ContinuedD
32、3239 91 (2016)6TABLE 2 ContinuedD3239 91 (2016)7TABLE 2 ContinuedD3239 91 (2016)8TABLE 2 ContinuedD3239 91 (2016)9TABLE 2 ContinuedD3239 91 (2016)10TABLE 2 ContinuedD3239 91 (2016)119. Procedure9.1 If the mass spectrometer has been in continuousoperation, no additional preparation is necessary befor
33、e ana-lyzing samples. However, if the spectrometer has been turnedon only recently, check its operation according to the manu-facturers instructions to ensure stability before proceeding.9.2 Obtain the mass spectrum of the sample, scanning frommass 76 to the high-mass end of the spectrum.10. Calcula
34、tions10.1 Recording Mass SpectrumRead peak heights and thecorresponding masses for all peaks in the spectrum of thesample. Use the data, along with sample identification, as inputto the computer.11. Precision and Bias11.1 The precision of this test method as obtained bystatistical examination of int
35、erlaboratory test results on asample having the composition given in Table 5, is as follows:11.1.1 RepeatabilityThe difference between successivetest results obtained by the same operator with the sameapparatus under constant operating conditions on identical testmaterial, would in the long run, in
36、the normal and correctoperation of the test method, exceed the values shown in Table5 only in one case in twenty.11.1.2 ReproducibilityThe difference between two singleand independent results, obtained by different operators work-ing in different laboratories on identical test material, would inthe
37、long run, in the normal and correct operation of the testmethod, exceed the values shown in Table 5 only in one casein twenty.NOTE 5If samples are analyzed that differ appreciably in compositionfrom the sample used for the interlaboratory study, this precision state-ment may not apply.11.2 BiasThe q
38、uantities determined are defined by theconditions employed in this empirical method, and a statementof bias is therefore not appropriate.12. Keywords12.1 aromatic; gas oil; mass spectrometry; petroleumD3239 91 (2016)12TABLE 3 PC-69-378 Test Spectrum for Gas Oil Aromatics AnalysisD3239 91 (2016)13TAB
39、LE 4 Mass Spectral Analysis of Aromatic FractionsPC-69-378 Test Spectrum for Gas Oil Aromatics AnalysisCalc. Ion Sums Volume %Monoaromatics:AlkylbenzenesNaphthenebenzenesDinaphthenebenzenes9703.9017.9778.28498.13.312.313.438.9Diaromatics:NaphthalenesAcenaphthenes,dibenzofuransFluorenes4774.6576.7809
40、.19158.6.59.010.726.2Triaromatics:PhenanthrenesNaphthenephenanthrenes6156.3470.9625.8.44.713.1Tetraaromatics:Pyrenes 3980.6070.5.48.390. Chrysenes 2090. 2.9Pentaaromatics:PerylenesDibenzanthracenes1293.366.1658.1.80.52.3Thiopheno Aromatics:BenzothiophenesDibenzothiophenesNaphthobenzothiophenes565.96
41、8.339.1872.0.81.30.52.6Unidentified Aromatics: 6322. 8.6Class I incl withNaphthenephenanthrenesClass II 614. 0.8Class III 838. 1.1Class IV 3431. 4.7Class V 546. 0.7Class VI 281. 0.4Class VII 612. 0.8TABLE 5 Precision Summary Based on Cooperative DataVol % rRr RAlkylbenzenes 13.7 0.3 1.0 1.2 3.0Napht
42、henebenzenes 13.3 0.1 1.1 0.5 3.3Dinaphthenebenzenes 13.7 0.2 0.4 0.9 1.1Naphthalenes 6.7 0.2 0.8 0.9 2.3Acenaphthenes/dibenzofurans 9.0 0.1 0.2 0.5 0.5Fluorens 10.7 0.1 0.2 0.3 0.6PhenanthrenesNaphthenephenanthrenes8.64.50.10.20.30.40.20.71.01.2PyrenesChrysenes5.72.80.10.20.50.40.30.51.61.1Perylene
43、sDibenzanthracenes1.70.40.10.10.20.10.30.20.60.4Benzothiophenes 1.0 0.2 0.4 0.8 1.1Dibenzothiophenes 1.5 0.1 0.3 0.3 0.8Naphthabenzothiophenes 0.5 0.1 0.3 0.3 1.0Class II Unidentified 0.4 0.1 0.4 0.3 1.1Class III Unidentified 0.6 0.1 0.4 0.4 1.2Class IV Unidentified 4.1 0.2 0.5 0.6 1.6Class V Uniden
44、tified 0.5 0.1 0.3 0.5 0.8Class VI Unidentified 0.2 0.1 0.1 0.3 0.4Class VII Unidentified 0.4 0.2 0.2 0.5 0.7r= repeatability standard deviationR= reproducibility standard deviationr = repeatabilityR = reproducibilityD3239 91 (2016)14ASTM International takes no position respecting the validity of an
45、y patent rights asserted in connection with any item mentionedin this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the riskof infringement of such rights, are entirely their own responsibility.This standard is subject to rev
46、ision at any time by the responsible technical committee and must be reviewed every five years andif not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standardsand should be addressed to ASTM International Headquarters. Your
47、 comments will receive careful consideration at a meeting of theresponsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you shouldmake your views known to the ASTM Committee on Standards, at the address shown below.This standard is copyr
48、ighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org). Permission rights to photocopy the standard may also be secured from the Copyright Clearance Center, 222Rosewood Drive, Danvers, MA 01923, Tel: (978) 646-2600; http:/ 91 (2016)15
