1、Designation: D5399 09 (Reapproved 2017)Standard Test Method forBoiling Point Distribution of Hydrocarbon Solvents by GasChromatography1This standard is issued under the fixed designation D5399; the number immediately following the designation indicates the year oforiginal adoption or, in the case of
2、 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 method covers the determination of the boilingpoint distribution of hydrocarbon solve
3、nts by capillary gaschromatography. This test method is limited to samples havinga minimum initial boiling point of 37C (99F), a maximumfinal boiling point of 285C (545F), and a boiling range of 5to 150C (9 to 270F) as measured by this test method.1.2 For purposes of determining conformance of an ob
4、-served or calculated value using this test method to relevantspecifications, test result(s) shall be rounded off “to the nearestunit” in the last right-hand digit used in expressing thespecification limit, in accordance with the rounding-off methodof Practice E29.1.3 The values stated in SI units a
5、re standard. The valuesgiven in parentheses are for information purposes only.1.4 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, health, and environmental pra
6、ctices and deter-mine the applicability of regulatory limitations prior to use.1.5 This international standard was developed in accor-dance with internationally recognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides a
7、nd Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D86 Test Method for Distillation of Petroleum Products andLiquid Fuels at Atmospheric PressureD850 Test Method for Distillation of Industrial AromaticHydro
8、carbons and Related MaterialsD1078 Test Method for Distillation Range of Volatile Or-ganic LiquidsD2887 Test Method for Boiling Range Distribution of Pe-troleum Fractions by Gas ChromatographyD2892 Test Method for Distillation of Crude Petroleum(15-Theoretical Plate Column)D3710 Test Method for Boil
9、ing Range Distribution of Gaso-line and Gasoline Fractions by Gas Chromatography(Withdrawn 2014)3E29 Practice for Using Significant Digits in Test Data toDetermine Conformance with SpecificationsE691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Test Method3. Termin
10、ology3.1 Definitions:3.1.1 initial boiling point (IBP), nthe point at which acumulative area count equal to 0.5 % of the total area under thechromatogram is obtained.3.1.2 final boiling point (FBP), nthe point at which acumulative area count equal to 99.5 % of the total area underthe chromatogram is
11、 obtained.4. Summary of Test Method4.1 The sample is introduced into a capillary gas chromato-graphic column that separates hydrocarbons in the order ofincreasing boiling point. The column temperature is raised at areproducible rate and the area under the chromatogram isrecorded throughout the run.
12、Boiling points are assigned froma calibration curve obtained under the same conditions byrunning a known mixture of hydrocarbons covering the boilingrange expected in the sample. From these data, the boilingpoint distribution of the sample is obtained.5. Significance and Use5.1 The gas chromatograph
13、ic determination of the boilingpoint distribution of hydrocarbon solvents can be used as an1This test method is under the jurisdiction of ASTM Committee D01 on Paintand Related Coatings, Materials, and Applications and is the direct responsibility ofSubcommittee D01.35 on Solvents, Plasticizers, and
14、 Chemical Intermediates.Current edition approved Dec. 1, 2017. Published December 2017. Originallyapproved in 1993. Last previous edition approved in 2009 as D5399 09. DOI:10.1520/D5399-09R17.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at ser
15、viceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3The last approved version of this historical standard is referenced onwww.astm.org.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken,
16、PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization
17、 Technical Barriers to Trade (TBT) Committee.1alternative to conventional distillation methods for control ofsolvents quality during manufacture, and specification testing.5.2 Boiling point distribution data can be used to monitorthe presence of product contaminants and compositional varia-tion duri
18、ng the manufacture of hydrocarbon solvents.5.3 Boiling point distribution data obtained by this testmethod are not equivalent to those obtained by Test MethodsD86, D850, D1078, D2887, D2892, and D3710.6. Apparatus6.1 ChromatographAny gas chromatograph that canhandle capillary column and has the foll
19、owing characteristics:6.1.1 DetectorA flame ionization detector (FID) capableof continuous operation at a temperature equivalent to themaximum column temperature employed.6.1.2 Column Temperature ProgrammerThe chromato-graph must be capable of reproducible linear temperatureprogramming over a range
20、sufficient to establish a retentiontime of 1 min for n-pentane and to allow elution of entiresample within a reasonable time period.6.1.3 Sample Inlet SystemThe sample inlet system mustbe capable of operating continuously at a temperature up to themaximum column temperature employed, or provide on-c
21、olumn injection.NOTE 1The use of cool, on-column injection using an automaticinjector or sampler has been shown to provide better precision relative tomanual injection.6.1.4 ColumnA10 to 30 m by 0.53 mm inside diameter by3-m bonded methyl silicone, fused silica, or equivalentcolumn that elutes compo
22、nents in order of boiling points, andmeets the resolution criteria specified in 8.2 must be used (see8.4).6.1.5 IntegratorMeans must be provided for determiningthe accumulated area under the chromatogram. This can bedone by means of a computer or electronic integrator. A timingdevice can be used to
23、record the area at set time intervals. Thesame basis for measuring time must be used to determine theretention times in the calibration, and the sample. The maxi-mum signal measured must be within the linear range of themeasuring system used.6.1.6 Flow ControllerThe chromatograph must beequipped wit
24、h a constant-flow device capable of maintainingthe carrier gas at a constant flow rate throughout the tempera-ture program.6.1.7 Sample IntroductionA microsyringe is required forthe introduction of the sample to the gas chromatograph (seeNote 1).7. Reagents and Materials7.1 Purity of ReagentsReagent
25、 grade chemicals shall beused in the preparation of the calibration mixture.7.2 Calibration MixtureA synthetic blend of pure liquidhydrocarbons of known boiling points. The components of thecalibration mixture are listed in Table 1 and prepared bymixing equivolume quantities of the components. At le
26、ast onecomponent in the mixture must have a boiling point equal to orlower than the initial boiling point of the sample, and onecomponent must have a retention time greater than anycomponent in the sample.7.3 Carrier Gas, Helium (high purity)Additional purifi-cation is recommended by the use of mole
27、cular sieves or othersuitable agents to remove water, oxygen, and hydrocarbons.7.3.1 Warning: Helium is a compressed gas under highpressure.7.4 Detector Gases, Air, Hydrogen (high purity)Additional purification for air and hydrogen is recommendedby the use of molecular sieves, activated carbons, or
28、othersuitable agents to remove water and organics.7.4.1 Warning: Air and hydrogen are compressed gasesunder high pressure. Hydrogen is an extremely flammable gas.8. Preparation of Apparatus8.1 Column PreparationThe column must be conditionedat the maximum operating temperature to reduce baseline shi
29、ftsdue to bleeding of column substrate.NOTE 2The column can be conditioned using the following proce-dure:(a) Disconnect the column from the detector,(b) Purge the column at ambient temperature with carriergas for at least 30 min,(c) With carrier gas flowing through the column, raise thecolumn tempe
30、rature to the maximum operating temperatureand maintain the temperature at this level for 12 to 16 h,(d) Cool the column to ambient temperature,(e) Reconnect the column to the detector,(f) Set the detector temperature to at least 5C higher thanthe maximum column temperature, and(g) Program the colum
31、n temperature up to the maximumseveral times with normal carrier flow until a stable, flatbaseline is obtained.8.2 Column ResolutionTo test column resolution, injectthe same volume of the calibration mixture as used duringnormal sample analysis and obtain the chromatogram by theprocedure described i
32、n Section 9. Using the n-dodecane (C12)and n-tridecane (C13) peaks, and Fig. 1, calculate theresolution, R, as calculated from the equation:R 5 2D/Y11Y2! (1)TABLE 1 Calibration MixturePeak Number Compound Identification Normal Boiling Point, C1 n-Pentane 36.12 2-Methyl Pentane 60.03 n-Hexane 68.94 2
33、,4-Dimethyl Pentane 80.65 n-Heptane 98.36 Toluene 110.67 n-Octane 125.68 p-Xylene 138.39 n-Propyl Benzene 159.410 n-Decane 173.911 n-Butyl Benzene 183.312 n-Dodecane 216.113 n-Tridecane 235.614 n-Tetradecane 253.915 n-Pentadecane 270.616 n-Hexadecane 287.2D5399 09 (2017)2where:D = time, s, between n
34、-C12and n-C13apexesY1= peak width of n-C12,sY2= peak width of n-C13,sThe resolution, R, thus calculated must be between eight andtwelve to be acceptable.8.3 Skewing of PeaksCalculate the ratio A/B on peaks inthe calibration mixture as shown in Fig. 2. Call the width inseconds of the part of the peak
35、 ahead of the time of the apex at5 % of peak height A, and call B to equal the width in secondsof the part of the peak after the time of the apex at 5 % of peakheight. This ratio must not be less than 0.5 nor more than 2.08.4 Typical instrument parameters are as follows:8.4.1 Column length equals 10
36、 to 30 m,8.4.2 Column material and size equal fused silica or glass,0.53 to 0.75 mm inside diameter,8.4.3 Liquid phase equals bonded methyl silicone orequivalent,8.4.4 Column film thickness equals 3 to 5 m,8.4.5 Initial column temperature equals 35C (95F),8.4.6 Initial hold equals 2 min,8.4.7 Progra
37、m rate equals 10 to 20C (18 to 36F)/min,8.4.8 Final temperature equals 225C (437F) to 280C(536F),8.4.9 Final time equals 2 min,8.4.10 Injector temperature equals cool, on-column,8.4.11 Detector temperature equals 250C (482F),8.4.12 Detector range (HP) equals 6 to 8,8.4.13 Carrier gas flow rate equal
38、s 8 to 10 mL/min, and8.4.14 Sample size equals 0.1 to 0.5 L.9. Procedure9.1 CalibrationAfter preparing the apparatus as in Section8, inject the calibration mixture into the gas chromatograph.Record the data in such a manner that the retention times ofpeak maxima and the peak areas for each component
39、 areobtained.9.1.1 The sample size of the calibration mixture must bechosen as to avoid distortion of the individual component peakshape caused by overloading the sample capacity of thecolumn. Distortion in retention time measurement and henceerrors in boiling point distribution will be likely with
40、columnoverloading. Sample size of 0.1 to 0.5 L have been shown togive good results.9.1.2 This test method requires the use of commerciallyavailable “Simulated Distillation” softwares4to process thechromatographic data in order to obtain good precision ofresults. Calibration of the gas chromatographi
41、c method can bedone by inputting the retention times, and the normal boilingpoints of each of the components of the calibration mixture.The equation for the temperature versus retention time calibra-tion curve is automatically generated by the software.9.1.3 Insure a rigorous syringe cleaning step b
42、etweensamples where multiple volumes of the next sample are flushedthrough the syringe and deposited to waste prior to actualinjection. If an autosampler or injector is used, the syringeflushing feature has to be programmed so that syringe carry-over is minimized. If injections are made manually, in
43、sure thatthe syringe needle is thoroughly wiped clean before injection.9.1.4 A typical calibration curve using a 30-m column isshown in Fig. 3.9.1.5 For best precision, make sure that the calibration curveis essentially a linear plot of boiling point versus retentiontime. It is essential that at lea
44、st one point on the calibrationcurve be at a lower boiling point than the IBP of the sample.Extrapolation of the curve at the upper end is more accurate,but for best accuracy, make sure that calibration points bracketthe boiling range of the sample at both the low and high ends.9.1.6 The calibration
45、 must be checked at least once a daywhen the instrument is in use.9.2 Sample AnalysisUsing identical instrument param-eters and conditions used in the calibration run, inject thesample into the gas chromatograph. Record the data in such amanner that the retention times and areas of chromatographicpe
46、aks are obtained.9.2.1 The same software used to process the calibration runmust be used to process the sample gas chromatographic data.The software must be able to process the data and report IBP,and FBP, as well as boiling point data for any percentrecovered (at 1 % interval) between the initial a
47、nd the finalboiling point.9.2.2 Care must be taken that the sample size chosen doesnot allow some peaks to exceed the linear range of the detector.4Beckman CALS Simulated Distillation software was used in developing thistest method. There are other Simulated Distillation softwares available in thema
48、rket. Such softwares are marketed by Hewlett Packard, Perkin Elmer-Nelson,Analytical Controls, VG, Separation Systems, and others.FIG. 1 Column ResolutionFIG. 2 Peak SkewnessD5399 09 (2017)3Choose the detector range and the sample size such that allpeaks are fully integrated.9.2.3 Baseline stability
49、 is generally not a problem for thesetypes of samples. If problems with baseline is encountered,constant attention must be given to all factors that influencebaseline stability such as column bleed, septum bleed, detectortemperature control, carrier gas flow, leaks, etc. Baselinecorrection is generally not required for these types of samples.9.2.4 Make periodic blank runs in the normal mannerwithout injection of sample to insure that the system is freefrom contamination. If the blank run shows sample carryovercontamination, steps must be
