1、Designation: D 5501 09An American National StandardStandard Test Method forDetermination of Ethanol Content of Denatured Fuel Ethanolby Gas Chromatography1This standard is issued under the fixed designation D 5501; the number immediately following the designation indicates the year oforiginal adopti
2、on 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. Scope*1.1 This test method covers the determination of the ethanolcontent of denatu
3、red fuel ethanol by gas chromatography.1.2 Ethanol is determined from 93 to 97 mass % andmethanol is determined from 0.01 to 0.6 mass %. Equationsused to convert these individual alcohols from mass % tovolume % are provided.1.3 This test method does identify and quantify methanolbut does not purport
4、 to identify all individual components thatmake up the denaturant.1.4 Water cannot be determined by this test method andshall be measured by a procedure such as Test Method D 1364and the result used to correct the chromatographic values.1.5 This test method is inappropriate for impurities that boila
5、t temperatures higher than 225C or for impurities that causepoor or no response in a flame ionization detector, such aswater.1.6 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.7 This standard does not purport to address all o
6、f 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 ASTM Standards:2D 1298 Test Method for
7、Density, Relative Density (SpecificGravity), or API Gravity of Crude Petroleum and LiquidPetroleum Products by Hydrometer MethodD 1364 Test Method for Water in Volatile Solvents (KarlFischer Reagent Titration Method)D 4052 Test Method for Density and Relative Density ofLiquids by Digital Density Met
8、erD 4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD 4307 Practice for Preparation of Liquid Blends for Use asAnalytical StandardsD 4626 Practice for Calculation of Gas ChromatographicResponse FactorsD 4806 Specification for Denatured Fuel Ethanol for Blend-ing with Gasolines fo
9、r Use as Automotive Spark-IgnitionEngine FuelE 355 Practice for Gas Chromatography Terms and Rela-tionshipsE 594 Practice for Testing Flame Ionization Detectors Usedin Gas or Supercritical Fluid ChromatographyE 1064 Test Method for Water in Organic Liquids byCoulometric Karl Fischer Titration3. Term
10、inology3.1 DefinitionsThis test method makes reference to manycommon gas chromatographic procedures, terms, and relation-ships. Detailed definitions can be found in Practices E 355 andE 594.4. Summary of Test Method4.1 A representative aliquot of the fuel ethanol sample isintroduced into a gas chrom
11、atograph equipped with a polydim-ethylsiloxane bonded phase capillary column. Helium carriergas transports the vaporized aliquot through the column wherethe components are separated by the chromatographic process.Components are sensed by a flame ionization detector as theyelute from the column. The
12、detector signal is processed by anelectronic data acquisition system. The ethanol and methanolcomponents are identified by comparing their retention times tothe ones identified by analyzing standards under identicalconditions. The concentrations of all components are deter-mined in mass percent area
13、 by normalization of the peak areas.5. Significance and Use5.1 Fuel ethanol is required to be denatured with gasoline inaccordance with Specification D 4806. State and federal lawsspecify the concentration of ethanol in gasoline blends. Thedetermination of the amount of denaturant is important to1Th
14、is test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.04.0L on Hydrocarbon Analysis.Current edition approved April 15, 2009. Published May 2009. Originallyapproved in 1994. Last previous edition approved
15、 in 2004 as D 550104.2For 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.1*A Summary of Changes section appears a
16、t the end of this standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.ensure the blended fuel complies with federal and state laws.This test method provides a method of determining thepercentage of ethanol (purity) of the fuel et
17、hanol that isblended into gasoline.6. Apparatus6.1 Gas Chromatograph, capable of operating at the condi-tions listed in Table 1. A heated flash vaporizing injectordesigned to provide a linear sample split injection (for ex-ample, 200:1) is required for proper sample introduction.Carrier gas controls
18、 shall be of adequate precision to providereproducible column flows and split ratios in order to maintainanalytical integrity. Pressure control devices and gauges shallbe designed to attain the linear velocity required in the columnused. A hydrogen flame ionization detector with associated gascontro
19、ls and electronics, designed for optimum response withopen tubular columns, is required.6.2 Sample IntroductionManual or automatic liquid sy-ringe sample injection to the splitting injector is employed.Devices capable of 0.1 to 0.5 L injections are suitable. Itshould be noted that inadequate splitte
20、r design, poor injectiontechnique, and overloading the column can result in poorresolution. Avoid overloading, particularly of the ethanol peak,and eliminate this condition during analysis.6.3 ColumnThis test method utilizes a fused silica opentubular column with non-polar polydimethylsiloxane bonde
21、d(cross-linked) phase internal coating.Any column with equiva-lent or better chromatographic efficiency and selectivity tothose described in 6.3.1 can be used.6.3.1 Open tubular column with a non-polar polydimethyl-siloxane bonded (cross-linked) phase internal coating, either150 m by 0.25 mm with a
22、1.0 m film thickness, or 100 m by0.25 mm with a 0.5 film thickness is required.6.4 Electronic Data Acquisition SystemAny data acquisi-tion and integration device used for quantification of theseanalyses must meet or exceed these minimum requirements:6.4.1 Capacity for at least 80 peaks/analysis,6.4.
23、2 Normalized percent calculation based on peak areaand using response factors,6.4.3 Identification of individual components based on re-tention time,6.4.4 Noise and spike rejection capability,6.4.5 Sampling rate for narrow (96 %ethanol, 0.1 % methanol and 3.9 % n-heptane. Calculate themass relative
24、response factor according to Practice D 4626.11. Gas Chromatographic Analysis Procedure11.1 Set the instrument operating variables. See Table 1 fortypical operating conditions.11.2 Set instrumental sensitivity such that any component ofat least 0.002 mass % can be detected and integrated.11.3 Inject
25、 0.1 to 0.5 L of sample into the injection portand start the analysis. Obtain a chromatogram and peakintegration report. A sample chromatogram is shown in Fig. 1.11.4 The ethanol peak will require tangential skimming tobe correctly integrated if components of the denaturant elute onthe ethanol peaks
26、 tail.12. Calculation12.1 Multiply the area of each identified peak by theappropriate mass relative response factor. Use those factorsdetermined for individual compounds and use a factor of 1.000for unknowns.12.2 Determine the relative mass percent of the individualalcohols by using the following eq
27、uation:RMi5ARi3 100ARt(2)where:RMi= relative mass % of the individual alcohols,ARi= area of the individual alcohol peak corrected by theappropriate mass relative response factor (see 12.1),andARt= total area of all detected peaks corrected by theirappropriate mass relative response factors (12.1 ).1
28、2.3 Obtain the mass % of water in the sample. TestMethods D 1364, E 1064, or equivalent, can be used.12.4 Determine the mass % of the alcohols of interest byusing the following equation:TABLE 2 Pertinent Component DataTypical Mass RelativeResponse FactorsARelative Density at15.56CMethanol 3.20 0.796
29、Ethanol 2.06 0.794Awhere n-heptane = 1.D5501093Mi5RMi3 100 2 mass % water in sample!100(3)where:Mi= mass % of the individual alcohol being determined,andRMi= relative mass % of the individual alcohol from Eq2.12.5 For the volumetric concentration of the alcohol, calcu-late as follows:Vi5Mi3 DsDi(4)w
30、here:Vi= volume % of component i,Mi= mass % of component i from Eq 3,Di= relative density at 15.56C of component i as foundin Table 2, andDs= sample under study as determined by Test MethodD 1298 or D 4052.13. Report13.1 Report the purity of the individual alcohols to thenearest 0.01 mass % using Eq
31、 3 or nearest 0.01 volume %using Eq 4.14. Precision and Bias14.1 PrecisionThe precision of this test method as deter-mined by the statistical examination of the interlaboratory gaschromatographic test results is as follows:14.1.1 RepeatabilityThe difference between successiveresults obtained by the
32、same operator with the same apparatusunder constant operating conditions on identical test materialswould, in the long run, in the normal and correct operation ofthe test method exceed the following values only in one case intwenty.RepeatabilityAComponent Range,Mass %Repeatability,Mass %Ethanol 9397
33、 0.21Methanol 0.010.6 0.01859 =XAwhere X is the mass percent.14.1.2 ReproducibilityThe difference between two singleand independent results obtained by different laboratories onidentical test material would, in the long run, exceed thefollowing values only in one case in twenty:ReproducibilityACompo
34、nent Range,Mass %Reproducibility,Mass %Ethanol 9397 0.53Methanol 0.010.6 0.1172 =XAwhere X is the mass percent.NOTE 2The data below shows repeatabilities and reproducibilities forethanol and several methanol values obtained using the formulas given in14.1.1 and 14.1.2.Calculated Precision Values for
35、 Ethanol and MethanolRepeatability Reproducibilityamount r amount REtOH for all resultswithin scope(93to97%)0.21 EtOH for all resultswithin scope(93to97%)0.53MeOH 0.01 0.00186 MeOH 0.01 0.011720.05 0.00416 0.05 0.026210.10 0.00588 0.10 0.037060.25 0.00930 0.25 0.058600.50 0.01315 0.50 0.082870.60 0.
36、01440 0.60 0.0907814.1.3 BiasNo significant difference was found betweenthe ethanol or methanol content obtained by this test methodand the expected ethanol or methanol content (based on theconcentrations of ethanol and methanol in the preparedsamples) for the fuel ethanol samples analyzed in the ro
37、undrobin used to evaluate the precision of this test method.415. Keywords15.1 denatured; ethanol; fuel grade gas chromatography4Supporting data have been filed at ASTM International Headquarters and maybe obtained by requesting Research Reports RR: D02-1266.FIG. 1 Sample ChromatogramD5501094SUMMARY
38、OF CHANGESSubcommittee D02.04.0L has identified the location of selected changes to this standard since the last issue(D 550104) that may impact the use of this standard.(1) Changed the lower end of the applicable range for metha-nol from 0.1 to 0.01 mass % in 1.2 to align with 14.1.1 and14.1.2.(2)
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42、 ASTM Committee on Standards, at the address shown below.This standard 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).D5501095
