1、Designation: D7319 13D7319 17Standard Test Method forDetermination of Existent and Potential Sulfate andInorganic Chloride in Fuel Ethanol and Butanol by DirectInjection Suppressed Ion Chromatography1This standard is issued under the fixed designation D7319; the number immediately following the desi
2、gnation 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 dir
3、ect injection ion chromatographic procedure for determining existent and potential inorganicsulfate and total inorganic chloride content in hydrous and anhydrous denatured ethanol and butanol to be used in motor fuelapplications. It is intended for the analysis of ethanol and butanol samples contain
4、ing between 1.01.0 mgkg to 20 mg/kg ofexistent or potential inorganic sulfate and 1.01.0 mgkg to 50 mg/kg of inorganic chloride.NOTE 1Tertiary butanol is not included in this test method. 1-butanol, 2-butanol, and isobutanol are included in the testing and research report forthis test method.1.2 The
5、 values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropri
6、ate safety safety, health, and healthenvironmental practices and determine theapplicability of regulatory limitations prior to use. Material Safety Data Sheets are available for reagents and materials. Reviewthem for hazards prior to usage.1.4 This international standard was developed in accordance
7、with internationally recognized principles on standardizationestablished in the Decision on Principles for the Development of International Standards, Guides and Recommendations issuedby the World Trade Organization Technical Barriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standard
8、s:2D1193 Specification for Reagent WaterD4052 Test Method for Density, Relative Density, and API Gravity of Liquids by Digital Density MeterD4057 Practice for Manual Sampling of Petroleum and Petroleum ProductsD4177 Practice for Automatic Sampling of Petroleum and Petroleum ProductsD5827 Test Method
9、 for Analysis of Engine Coolant for Chloride and Other Anions by Ion ChromatographyD6299 Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measure-ment System PerformanceD6792 Practice for Quality Management Systems in Petroleum Products, Liqu
10、id Fuels, and Lubricants Testing LaboratoriesD7318 Test Method for Existent Inorganic Sulfate in Ethanol by Potentiometric TitrationD7328 Test Method for Determination of Existent and Potential Inorganic Sulfate and Total Inorganic Chloride in Fuel Ethanolby Ion Chromatography Using Aqueous Sample I
11、njection2.2 European Norm Standards:3EN 15492 Ethanol as a blending component for petrol - Determination petrolDetermination of inorganic chloride and sulfatecontent - Ion contentIon chromatographic method3. Terminology3.1 Definitions of Terms Specific to This Standard:1 This test method is under th
12、e jurisdiction ofASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of SubcommitteeD02.03 on Elemental Analysis.Current edition approved May 1, 2013Oct. 1, 2017. Published August 2013October 2017. Originally approved in 2007. Last previous edition
13、 approved in 20122013 asD7319 12.D7319 13. DOI: 10.1520/D7319-13.10.1520/D7319-17.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page
14、 on the ASTM website.3 Available from American National Standards Institute (ANSI), 25 W. 43rd St., 4th Floor, New York, NY 10036, http:/www.ansi.org.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the
15、 previous version. Becauseit may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.*A Summary o
16、f Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States13.1.1 existent inorganic sulfate, ninorganic sulfate species actually present in the sample at the time of analysis with nooxidation
17、treatment.3.1.2 inorganic chloride, nchloride present as hydrochloric acid, ionic salts of this acid, or mixtures of these.3.1.3 inorganic sulfate, nsulfate (SO4-2) species present as sulfuric acid, ionic salts of this acid, or mixtures of these.3.1.4 potential sulfate, ninorganic sulfate species pr
18、esent after the sample has been reacted with an oxidizing agent.4. Summary of Test Method4.1 For existent inorganic sulfate and total chloride, a small volume of an ethanol or butanol sample is directly injected into asuitably configured ion chromatograph in accordance with manufacturers recommendat
19、ions for this test method. For potentialsulfate, 0.5 mL of 30 % hydrogen peroxide solution is added to 9.5 mL of the ethanol or butanol sample, and then injected intothe ion chromatograph. Ions are separated based on their affinity for exchange sites of the resin with respect to the resins affinityf
20、or the eluent. The suppressor increases the sensitivity of the test method by both increasing the conductivity of the analytes anddecreasing the conductivity of the eluent. It also converts the eluent and analytes to the corresponding hydrogen forms of anions.Anions are quantified by integration of
21、their responses compared with an external calibration curve, and are measured asmilligrams/litre, then converted to milligrams/kilograms. The calibration standards are prepared in an aqueous matrix.4.1.1 The use of acid suppression technology is more significant for the precision of sulfate measurem
22、ent than for chloride.Sulfate precision will be worse if acid suppression is not used.4.2 Similar methods for chloride and sulfate determinations can be found in EN 15492 for total chloride, in Test Method D7328for total chloride and existent and potential inorganic sulfate by ion chromatography wit
23、h aqueous sample injection, and in TestMethod D7318 for existent inorganic sulfate by potentiometric lead titration and Test Method D5827 for chloride and other anionsin engine coolants by ion chromatography.NOTE 2Butanol has limited solubility in water, do not dilute samples with water prior to ana
24、lysis. In addition, any remnant water from the sampledelivery device or glassware may lead to low recoveries of sulfate and chloride. Avoid unintended water contamination of the sample. Added water canlead to phase separation of the sample. The chloride and sulfate ions can migrate to the water domi
25、nate phase and lower the recovery from the butanol.5. Significance and Use5.1 Sulfates and chlorides can be found in filter plugging deposits and fuel injector deposits. The acceptability for use of thefuel components and the finished fuels depends on the sulfate and chloride content.5.2 Existent an
26、d potential inorganic sulfate and total chloride content, as measured by this test method, can be used as onemeasure of the acceptability of gasoline components for automotive spark-ignition engine fuel use.6. Interferences6.1 Interferences can be caused by substances with similar ion chromatographi
27、c retention times, especially if they are in highconcentration compared to the analyte of interest. Sample dilution can be used to minimize or resolve most interference problems.6.2 A water dip (system void, negative peak as shown in Fig. 1) can cause interference with some integrators. Usually, for
28、chloride and sulfate determinations, the water dip should not be a problem since the chloride and sulfate peaks are far away fromthe water dip.6.3 Given the trace amounts of chloride and sulfate determined in this test method, interferences can be caused by contaminationof glassware, eluent, reagent
29、s, and the like. For example, sodium leaching from glassware can precipitate with sulfate giving lowsulfate results. Take care to ensure that contamination is kept at the lowest possible levels. The use of powder-free gloves is highlyrecommended to prevent sample contamination.7. Apparatus7.1 Analyt
30、ical Balance, capable of weighing up to 100 g accurately to 0.0001 g.7.2 Drying Oven, controlled at 110110 C 6 5C5 C for drying sodium sulfate and sodium chloride.7.3 Desiccator, containing freshly activated silica gel (or equivalent desiccant) with moisture content indicator.7.4 Pipets or Volumetri
31、c Transferring Devices, appropriately sized Class A glass pipets or their equivalent or variable volumeautomatic pipets fitted with disposable polypropylene tips.7.5 Volumetric Flasks (with Glass Stoppers), Class A of 10, 25, 50, 100, 1000, 2000cc10 mL, 25 mL, 50 mL, 100 mL,1000 mL, 2000 mL capacity
32、.7.5.1 Container, equipped with a closure to prevent ethanol evaporation, 1 L (for sample collection). See 6.3 for additionalinformation.7.6 Ion Chromatograph, analytical system with all required accessories including syringes, columns, suppressor, and detectorwhich can be demonstrated to obtain the
33、 precision and detection limits and requirements of the method.D7319 1727.6.1 Injection System, capable of delivering 20 L with a precision better than 1 %, or as recommended for this determinationby the manufacturer.7.6.2 Pumping System, capable of delivering mobile phase flows between 0.20.2 mLmin
34、 and 2.5 mL/min with a precisionbetter than 2 %, or as recommended for this determination by the manufacturer.7.6.3 Guard Column, for protection of the analytical column from strongly retained constituents. Better separations are obtainedwith additional theoretical plates.7.6.4 Anion Separator Colum
35、n, 100 % solvent compatible and capable of producing satisfactory analyte (sulfate and chloride)separation (Fig. 1).7.6.5 Anion Suppressor Device, vendor specific and capable of using acid suppression technology.7.6.5.1 Tri-Chamber Approach, 100 % solvent compatible tri-chamber micro packed bed with
36、 cation exchange resin (orequivalent). Suppressor device should simultaneously be on-line continuously chemically regenerated to its hydrogen form usingany mineral acid providing H+ ion.7.6.5.2 Continuous Approach, The regenerant channels are flushed with a mineral acid (sulfuric) to supply hydroniu
37、m ionsrequired for the suppression reaction. The solvent compatible ion exchange membranes provide the transport pathway for thehydronium ions into the eluent channel and the transport of sodium and other cations out of the eluent channel.7.6.6 Conductivity Detector, (low volume), temperature contro
38、lled to 0.01C,0.01 C, capable of at least 00 Scm to10001000 S S/cm cm on a linear scale.7.6.7 Integrator or Chromatography Data System Software, capable of measuring peak areas and retention times, and correctingthe data in accordance with the baseline of the chromatogram.7.7 Gloves, powder-free exa
39、mination type.8. Reagents8.1 Purity of ReagentsReagent grade or higher purity chemicals shall be used for the preparation of all samples, standards,eluent, and regenerator solutions. Unless otherwise indicated, it is intended that all reagents conform to the specifications of theCommittee onAnalytic
40、al Reagents of theAmerican Chemical Society, where such specifications are available.4 Other grades maybe used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its use without lessening the accuracyof the determination.4 Reagent Chemicals, American Chemical
41、 Society Specifications, American Chemical Society, Washington, DC. For Suggestions on the testing of reagents not listed bythe American Chemical Society, see Annual Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and NationalFormulary, U.S. Phar
42、macopeial Convention, Inc. (USPC), Rockville, MD.NOTE 1Chromatogram retention times may be different depending on instruments or columns used.FIG. 1 Typical Ion Chromatogram of a Solution Containing 1 mg/L of Various Anions in WaterD7319 1738.2 Purity of WaterUnless otherwise indicated, reference to
43、 water shall be understood to mean reagent water as defined byType III or better in Specification D1193. For eluent preparation and handling, comply with all ion chromatograph instrument andcolumn vendor requirements (for example, filtering, degassing, and the like).8.3 Eluent Buffer Stock SolutionS
44、odium bicarbonate (NaHCO3) 1.0 mM 1.0 mM and sodium carbonate (Na2CO3) 3.2 mM.3.2 mM. Dissolve 8.48.4 g 6 0.0005 g 0.0005 g of NaHCO3 and 33.9233.92 g 6 0.0005 g 0.0005 g of Na2CO3 in reagent waterin a 1-L1 L Type A volumetric flask and dilute to volume. Dilute 10.0 mL 10.0 mL of this stock solution
45、 to 1 L 1 L in a 1-L1 LType A volumetric flask with degassed reagent water. The eluent solution used may be different if other system or analyticalcolumns are used.NOTE 3Other volumes of stock solution can be prepared using appropriate ratios of reagents. Follow the specific guidelines for this solu
46、tion fromthe vendor of the column being used. Alternatively, this solution can be purchased from a qualified vendor.8.4 Suppressor Regenerant Solution for Suppressor0.1 M 0.1 M sulfuric acid. Carefully add 334 mL334 mLof reagent gradesulfuric acid (relative density 1.84) to approximately 500 mL500 m
47、Lreagent water in a 1-L1 Lvolumetric flask. (WarningThiswill generate a very hot solution.Allow it to cool before diluting to 1000 mLvolume. Never add water to concentrated acid.) Diluteto 1000 mL1000 mLwith reagent water, and label this solution as 10.0 M sulfuric acid. Dilute 10.0 mLof this concen
48、trate to 1000mL with reagent water for the final 0.1 M working suppressor solution. The regenerate solution used may be different if othersystem or analytical columns are used.NOTE 4Other volumes of this solution can be prepared using appropriate ratios of reagents. Follow the specific guidelines fo
49、r this solution from thevendor of the suppressor being used.8.5 Sodium Sulfateanhydrous, reagent grade, 99 % minimum purity. (WarningDo not ingest.Avoid unnecessary exposure.)8.6 Sodium ChlorideACS or reagent grade, 99 % minimum purity.8.7 Tetrabutylamonium BisulfateTechnical or reagent grade, 99 % minimum purity.8.8 Tetrabutylammonium ChlorideTechnical or reagent grade 97 % minimum purity.8.9 ButanolACS, 99 % minimum purity. Could consist of isobutanol, sec butanol, or n-butanol. (WarningFlammable,toxic, and may be harmful if ingested
