1、Designation: D 3239 91 (Reapproved 2006)An American National StandardStandard Test Method forAromatic Types Analysis of Gas-Oil Aromatic Fractions byHigh Ionizing Voltage Mass Spectrometry1This standard is issued under the fixed designation D 3239; the number immediately following the designation in
2、dicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method2covers the determinati
3、on by highionizing voltage, low resolution mass spectrometry of 18aromatic hydrocarbon types and 3 aromatic thiophenotypes instraight run aromatic petroleum fractions boiling within therange from 205 to 540C (400 to 1000F) (corrected toatmospheric pressure). Samples must be nonolefinic, mustcontain
4、not more than 1 mass % 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 ot
5、her compound types in the 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 purp
6、oses only.1.3 This standard 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. Re
7、ferenced Documents2.1 ASTM Standards:3D 2549 Test Method for Separation of Representative Aro-matics and Nonaromatics Fractions of High-Boiling Oilsby Elution ChromatographyD 2786 Test Method for Hydrocarbon Types Analysis ofGas-Oil Saturates Fractions by High Ionizing VoltageMass SpectrometryE 137
8、Practice for Evaluation of Mass Spectrometers forQuantitative Analysis from a Batch Inlet43. Terminology3.1 Definitions of Terms Specific to This Standard:3.1.1 Characteristic Mass Summations Classes IVII:3.1.2 Class I:(78 5 78 1 92 1 106 1 120 1 to end, polyisotopic1 91 1 105 1 119 1 to end, monois
9、otopic (1)3.1.3 Class II:(104 5 104 1 118 1 132 1 146 1 to end, polyisotopic1 117 1 131 1 145 1 to end, monoisotopic (2)3.1.4 Class III:(129 5 130 1 144 1 158 1 172 1 to end, polyisotopic1 129 1 143 1 157 1 171 1 to end, monoisotopic (3)3.1.5 Class IV:(128 5 128 1 142 1 156 1 170 1 to end, polyisoto
10、pic1 141 1 155 1 169 1 to end, monoisotopic (4)3.1.6 Class V:(154 5 154 1 168 1 182 1 196 1 to end, polyisotopic1 167 1 181 1 195 1 to end, monoisotopic (5)3.1.7 Class VI:(166 5 166 1 180 1 194 1 208 1 to end, polyisotopic1 179 1 193 1 207 1 to end, monoisotopic (6)3.1.8 Class VII:(178 5 178 1 192 1
11、 206 1 220 1 to end, polyisotopic1 191 1 205 1 219 1 to end, monoisotopic (7)3.1.9 Classes, Compound Types, Empirical FormulaeSeeTable 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 s
12、ummation of peaks most charac-teristic of each class. Calculations are carried out by the use ofa 7 by 7 inverted matrix derived from published spectra of purearomatic compounds. Each summation of peaks includes the1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Product
13、s and Lubricants and is the direct responsibility of SubcommitteeD02.04 on Hydrocarbon Analysis.Current edition approved May 1, 2006. Published June 2006. Originallyapproved in 1973. Last previous edition approved in 2001 as D 3239 91 (2001).2Robinson, C. J., and Cook, G. L., Analytical Chemistry (A
14、NCHA), 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.4Withdrawn.1Copyright ASTM Intern
15、ational, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.polyisotopic homologous series that contains molecular ionsand the monoisotopic homologous series one mass unit lessthan the molecular ion series. Using characteristic summationsfound in the monoisotopic mol
16、ecular 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 MethodD 2549).NOTE 2Monoisotopic peaks h
17、eights 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 h
18、ydrocarbon composition of processstreams and petroleum products boiling within the range 205 to540C (400 to 1000F) is useful in following the effect ofchanges in process variables, diagnosing the source of plantupsets, and in evaluating the effect of changes in compositionon product performance prop
19、erties. This method, when usedtogether with Test Method D 2786, provides a detailed analysisof the hydrocarbon composition of such materials.6. Apparatus6.1 Mass SpectrometerThe suitability of the mass spec-trometer to be used with this method shall be proven byperformance tests described both herei
20、n and in Practice E 137.6.2 Sample Inlet SystemAny inlet system may be usedthat permits the introduction of the sample without loss,contamination, or change in composition. The system mustfunction in the range from 125 to 350C to provide anappropriate sampling device.6.3 Microburet or Constant-Volum
21、e 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 Electr
22、onic 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 har
23、m-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 perm
24、it a scan over the massrange from 78 to 700. An ionizing voltage of 70 eV and anionizing current in the range from 10 to 70 A is used.NOTE 3The instrument conditions and calibration equations de-scribed in this method are based on the use of a 180 magnetic-deflectiontype mass spectrometer (CEC Model
25、 21-103). Satisfactory results havebeen obtained with some other magnetic deflection instruments. It is notknown if the equations are suitable for use on all other mass spectrometertypes.8.1.2 Computer ProgramThe FORTRAN program givenin Table 2 contains all the equations for calculating theanalysis,
26、 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 input for
27、mat 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. Thes
28、e are permitted provided that thealtered program gives the results shown in Table 4 with theinput data of Table 3.NOTE 4The program, as shown in Table 2, has run satisfactorily onIBM System 360 computers.9. Procedure9.1 If the mass spectrometer has been in continuous opera-tion, no additional prepar
29、ation is necessary before analyzingsamples. However, if the spectrometer has been turned on onlyrecently, check its operation according to the manufacturersinstructions to ensure stability before proceeding.9.2 Obtain the mass spectrum of the sample, scanning frommass 76 to the high-mass end of the
30、spectrum.TABLE 1 Classes, Compound Types, and Empirical FormulaeClass Type FormulaI 0 alkylbenzenes, CnH2n-6I 1 benzothiophenes, CnH2n-10SI 2 naphthenephenanthrenes,CnH2n-20II 0 naphthenebenzenes, CnH2n-8II 1 pyrenes, CnH2n-22II 2 unidentifiedIII 0 dinaphthenebenzenes, CnH2n-10III 1 chrysenes, CnH2n
31、-24III 2 unidentifiedIV 0 naphthalenes, CnH2n-12IV 1 dibenzothiophenes, CnH2n-16SIV 2 unidentifiedV 0 acenaphthenes + dibenzofurans,CnH2n-14and CnH2n-16OVV12perylenes, CnH2n-28unidentifiedVI 0 fluorenes, CnH2n-16VI 1 dibenzanthracenes, CnH2n-30VI 2 unidentifiedVII 0 phenanthrenes, CnH2n-18VII 1 naph
32、thobenzothiophenes, CnH2n-22SVII 2 unidentifiedD 3239 91 (2006)2TABLE 2 High Ionizing Voltage, Low Resolution 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.
33、D 3239 91 (2006)3TABLE 2 ContinuedD 3239 91 (2006)4TABLE 2 ContinuedD 3239 91 (2006)5TABLE 2 ContinuedD 3239 91 (2006)6TABLE 2 ContinuedD 3239 91 (2006)7TABLE 2 ContinuedD 3239 91 (2006)8TABLE 2 ContinuedD 3239 91 (2006)9TABLE 2 ContinuedD 3239 91 (2006)10TABLE 2 ContinuedD 3239 91 (2006)1110. Calcu
34、lations10.1 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 i
35、nterlaboratory 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, i
36、n 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 inth
37、e 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
38、 quantities 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; petroleumD 3239 91 (2006)12TABLE 3 PC-69-378 Test Spectrum for Gas Oil Aromatics AnalysisD 3239 91 (2006)1
39、3TABLE 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.
40、7809.19158.6.59.010.726.2Triaromatics: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:BenzothiophenesDibenzothiophenesNaphthobenzothiophenes56
41、5.968.339.1872.0.81.30.52.6Unidentified 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 % srsRr RAlkylbenzenes 13.7 0.3 1.0 1.2 3.
42、0Naphthenebenzenes 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 0.6PhenanthrenesNaphthenephenanthrenes8.64.50.10.20.30.40.20.71.01.2PyrenesChrysenes5.72.80.10.20.50.40.30.51.61.1Pe
43、rylenesDibenzanthracenes1.70.40.10.10.20.10.30.20.60.4Benzothiophenes 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
44、Unidentified 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 0.7sr= repeatability standard deviationsR= reproducibility standard deviationr = repeatabilityR = reproducibilityD 3239 91 (2006)14ASTM International takes no position respecting the valid
45、ity of any 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 subje
46、ct to revision 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 Headquart
47、ers. Your 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
48、 is copyrighted 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).D 3239 91 (2006)15
