ASTM_D_5599_-_15.pdf

Designation:D559915Standard Test Method forDetermination of Oxygenates in Gasoline by GasChromatography and Oxygen Selective Flame IonizationDetection1This standard is issued under the fixed designation D5599;the number immediately following the designation indicates 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()indicates an editorial change since the last revision or reapproval.1.Scope*1.1 This test method covers a gas chromatographic proce-dure for the quantitative determination of organic oxygenatedcompounds in gasoline having a final boiling point not greaterthan 220 C and oxygenates having a boiling point limit of130 C.It is applicable when oxygenates are present in the0.1%to 20%by mass range.1.2 This test method is intended to determine the massconcentration of each oxygenate compound present in a gaso-line.This requires knowledge of the identity of each oxygenatebeing determined(for calibration purposes).However,theoxygen-selective detector used in this test method exhibits aresponse that is proportional to the mass of oxygen.It is,therefore,possible to determine the mass concentration ofoxygen contributed by any oxygenate compound in the sample,whether or not it is identified.Total oxygen content in agasoline may be determined from the summation of theaccurately determined individual oxygenated compounds.Thesummed area of other,uncalibrated or unknown oxygenatedcompounds present,may be converted to a mass concentrationof oxygen and summed with the oxygen concentration of theknown oxygenated compounds.1.3 The values stated in SI units are to be regarded asstandard.No other units of measurement are included in thisstandard.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 and health practices and determine the applica-bility of regulatory limitations prior to use.2.Referenced Documents2.1 ASTM Standards:2D1744 Test Method for Determination of Water in LiquidPetroleum Products by Karl Fischer ReagentD4175 Terminology Relating to Petroleum,PetroleumProducts,and LubricantsD4307 Practice for Preparation of Liquid Blends for Use asAnalytical StandardsE594 Practice for Testing Flame Ionization Detectors Usedin Gas or Supercritical Fluid ChromatographyE1064 Test Method for Water in Organic Liquids by Coulo-metric Karl Fischer TitrationE1510 Practice for Installing Fused Silica Open TubularCapillary Columns in Gas Chromatographs3.Terminology3.1 Definitions:3.1.1 independent reference standardscalibration samplesof the oxygenates which are purchased or prepared frommaterials independent of the quality control check standardsand used for intralaboratory accuracy.3.1.2 oxygenate,nan oxygen-containing compound,suchas an alcohol or ether,which may be used as a fuel or fuelsupplement.3.1.3 quality control check standardscalibration samplesof the oxygenates for intralaboratory repeatability.4.Summary of Test Method4.1 An internal standard of a noninterfering oxygenate,forexample,1,2-dimethoxyethane(ethylene glycol dimethylether)is added in quantitative proportion to the gasolinesample.A representative aliquot of the sample and internal1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products,Liquid Fuels,and Lubricants and is the direct responsibility ofSubcommittee D02.04.0L on Gas Chromatography Methods.Current edition approved June 1,2015.Published July 2015.Originally approvedin 1994.Last previous edition approved in 2010 as D5599 00(2010).DOI:10.1520/D5599-15.2For 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.*A Summary of Changes section appears at the end of this standardCopyright ASTM International,100 Barr Harbor Drive,PO Box C700,West Conshohocken,PA 19428-2959.United States1 standard is injected into a gas chromatograph equipped with acapillary column operated to ensure separation of the oxygen-ates.Hydrocarbons and oxygenates are eluted from thecolumn,but only oxygenates are detected with the oxygen-selective flame ionization detector(OFID).Adiscussion of thisdetector is presented in Section 6.4.2 Calibration mixtures are used for determining the reten-tion times and relative mass response factors of the oxygenatesof interest.Suggested calibrant materials are listed in 8.2.4.3 The peak area of each oxygenate in the gasoline ismeasured relative to the peak area of the internal standard.Aquadratic least-squares fit of the calibrated data of eachoxygenate is applied and the concentration of each oxygenatecalculated.NOTE1While 1,2-dimethoxyethane has been found to be an appro-priate internal standard,other oxygenates may be used provided they are