ASTM D7359-2013 2500 Standard Test Method for Total Fluorine Chlorine and Sulfur in Aromatic Hydrocarbons and Their Mixtures by Oxidative Pyrohydrolytic Combustion followed by Ion .pdf

1、Designation: D7359 13Standard Test Method forTotal Fluorine, Chlorine and Sulfur in AromaticHydrocarbons and Their Mixtures by OxidativePyrohydrolytic Combustion followed by IonChromatography Detection (Combustion IonChromatography-CIC)1This standard is issued under the fixed designation D7359; the

2、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. Sc

3、ope*1.1 This test method covers the individual determination oftotal fluorine, chlorine and sulfur in aromatic hydrocarbons andtheir mixtures. Samples containing 0.10 to 50 mg/kg of eachelement can be analyzed.1.2 This method can be applied to sample types outside therange of the scope by dilution o

4、f the sample in an appropriatesolvent to bring the total concentrations of fluorine, chlorineand sulfur within the range covered by the test method.However, it is the responsibility of the analyst to verify thesolubility of the sample in the solvent and that the dilutedsample results conform to the

5、precision and accuracy of themethod.1.3 In determining the conformance of the test results usingthis method to applicable specifications, results shall berounded off in accordance with the rounding-off method ofPractice E29.1.4 The values stated in SI units are to be regarded asstandard. No other un

6、its of measurement are included in thisstandard.1.5 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 reg

7、ulatory limitations prior to use. See Section 8.2. Referenced Documents2.1 ASTM Standards:2D1193 Specification for Reagent WaterD6809 Guide for Quality Control and Quality AssuranceProcedures for Aromatic Hydrocarbons and Related Ma-terialsE29 Practice for Using Significant Digits in Test Data toDet

8、ermine Conformance with Specifications2.2 Other Documents:OSHA Regulations, 29 CFR paragraphs 1910.1000 and1910.120033. Summary of Test Method3.1 A sample of known weight or volume is placed into asample boat and introduced at a controlled rate into a hightemperature combustion tube. There the sampl

9、e is combustedin an oxygen rich pyrohydrolytic environment. The gaseousby-products of the combusted sample are trapped in anabsorption medium where the hydrogen halides (HX) formedduring combustion disassociate into their respective ions, X-while the sulfur oxides (SOX) formed are further oxidized t

10、oSO42-in the presence of an oxidizing agent. An aliquot ofknown volume of the adsorbing solution is then automaticallyinjected into an ion chromatograph (IC) by means of a sampleinjection valve. The halide and sulfate anions are separated intoindividual elution bands on the separator column of the I

11、C. Theconductivity of the eluent is reduced with an anion suppression1This test method is under the jurisdiction of ASTM Committee D16 onAromatic Hydrocarbons and Related Chemicals and is the direct responsibility ofSubcommittee D16.04 on Instrumental Analysis.Current edition approved July 15, 2013.

12、 Published September 2013. Originallyapproved in 2008. Last previous edition approved in 2008 as D7359 08. DOI:10.1520/D7359-13.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume informatio

13、n, refer to the standards Document Summary page onthe ASTM website.3Available from U.S. Government Printing Office Superintendent of Documents,732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401, http:/www.access.gpo.gov.*A Summary of Changes section appears at the end of this standardCopyr

14、ight ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1device prior to the ion chromatographs thermal conductivitydetector, where the anions of interest are measured. Quantifi-cation of the fluorine, chlorine and sulfur in the originalcombusted s

15、ample is achieved by first calibrating the systemwith a series of standards containing known amounts offluorine, chlorine and sulfur and then analyzing unknownsamples under the same conditions as the standards. Thecombined system of pyrohydrolytic combustion followed byion chromatographic detection

16、is referred to as Combustion IonChromatography (CIC).4. Significance and Use4.1 The total fluorine, chlorine and sulfur contained inaromatic hydrocarbon matrices can contribute to emissions, beharmful to many catalytic chemical processes, and lead tocorrosion. This test method can be used to determi

17、ne totalsulfur and halogens aromatic hydrocarbon matrices, in finishedproducts and can be used for compliance determinations whenacceptable to a regulatory authority using performance basedcriteria.5. Interferences5.1 Substances that co-elute with the anions of interest willinterfere. A high concent

18、ration of one anion can interfere withother constituents if their retention times are close enough toaffect the resolution of their peak.6. Apparatus6.1 Autosampler (Optional), capable of accurately deliver-ing 10 to 80 L of sample into the sample boat. Theautosampler may be used as long as the accu

19、racy and perfor-mance of the method is not degraded.NOTE 1Multiple rinsing with clean solvent between sample injectionsand/or sampling between different sample vials to minimize carryovercontamination from previous samples is recommended. A solvent flushfrom a vial separate from the solvent wash, pr

20、oviding clean, uncontami-nated solvent may also be used. These features may be used as long asthey do not degrade the performance and accuracy of the method.6.2 Balance, analytical, with sensitivity to 0.0001 g.6.3 Boat Inlet SystemThe system provides a sampling portfor the introduction of liquid an

21、d solid samples into the sampleboat and is connected to the inlet of the PyrohydrolyticCombustion Tube. The system is swept by a humidified inertcarrier gas and shall be capable of allowing the quantitativedelivery of the material to be analyzed into the pyrohydrolyticoxidation zone at a controlled

22、and repeatable rate.6.4 Boat Inlet Cooler (Optional)Sample volatility andinjection volume may require an apparatus capable of coolingthe sample boat prior to sample introduction. Thermoelectriccoolers (peltier) or recirculating refrigerated liquid devices arestrongly recommended. Switching sample bo

23、ats between eachanalysis may prove effective, provided sample size is not toolarge.6.5 Flow ControlThe apparatus must be equipped withflow controllers capable of maintaining a constant supply andflow of oxygen and argon gas.6.6 Furnace which can maintain a minimum temperature of900C.6.7 Gas Adsorpti

24、on Unit, having an adsorption tube ofeither 10 or 20 mL which is automatically filled with a knownvolume of absorption solution by a built-in burette or othersimilar device. The GasAdsorption Unit is interfaced to the IonChromatograph and injects an aliquot of the adsorption solu-tion into the Ion C

25、hromatograph after the sample is combustedand the by-products of combustion are absorbed. The GasAdsorption Unit rinses out the gas lines with Type I reagentwater (7.2) from the pyrohydrolytic combustion tube after thecompletion of the sample combustion to ensure all the com-bustion by-products (HX

26、and SO2) are absorbed. The GasAdsorption Unit rinses the gas lines and adsorption tube withType I reagent water (7.2) prior to sample combustion and afterthe absorption solution is injected into the Ion Chromatographto minimize cross contamination from the previous analysis.6.8 Gas-Tight Sampling Sy

27、ringe, capable of accurately de-livering 10 to 80 L of standard or sample.6.9 Pyrohydrolytic Combustion Tube made of quartz andconstructed such that when the sample is combusted in thepresence of humidified oxygen, the by-products of combustionare swept into the humidified pyrohydrolytic combustion

28、zone.The inlet end shall allow for the stepwise introduction andadvancement of a sample boat into the heated zone and shallhave a side arm for the introduction of the humidified carriergas and oxygen. The pyrohydrolytic combustion tube must beof ample volume, and have a heated zone with quartz wool

29、orother suitable medium providing sufficient surface area so thatthe complete pyrohydrolytic combustion of the sample isensured.6.10 Humidifier Delivery System, capable of deliveringType 1 reagent water (7.2) to the combustion tube at acontrolled rate sufficient to provide a pyrohydrolytic environ-m

30、ent.6.11 Ion Chromatograph (IC)4, equipped with:6.11.1 High Performance inert PEEK-(polyetheretherketone) flow path system is required.6.11.2 High Pressure eluent pump, capable of delivering 0.0to 5 mL/min (without eluent generator; 0.1 to 3 mL/min (witheluent generator), in 0.01 mL/min increments.

31、Flow rateaccuracy of 290Equivalents/column with alkanol quartenary ammoniumfunctional groups.4Many different companies manufacture automatic ion chromatographs. Consultthe manufacturer for details in setup and operation. Other systems may be used aslong as precision is shown to be as good as or bett

32、er than the precision in themethod.D7359 1326.11.6 Guard Column AG11HC (4X50mm) or equivalent,packed with same material for protection of the anion separatorcolumn and constructed of PEEK.6.11.7 Post-Column Chemical Suppression Device, capableof reducing the absolute conductivity of eluent concentra

33、tionsof up to 200 mM KOH (or NaOH). Delivery of hydronium ionsfor suppression by electrolysis of recycled eluent through acation exchange membrane.6.11.8 Eluent Generator (Optional), an eluent generatorcapable of producing eluents of 10 to 100 mM KOH withcontinuous eluent purification can be employe

34、d.6.11.9 Data Acquisition System, such as an integrator orcomputer data handling system capable of integrating the peakareas of ion chromatograph.6.12 Quartz or Ceramic Sample Boats of sufficient size tohold 10 to 80 L or mg of sample.7. Reagents and Materials7.1 Purity of ReagentsReagent grade chem

35、icals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specification of the Committeeon Analytical Reagents of the American Chemical Society,where such specifications are available.5Other grades may beused, provided that the reagent is of su

36、fficiently high purity topermit its use without lessening the accuracy of the determi-nation.7.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean Type 1 conforming toSpecification D1193.7.3 Quartz Wool, (fine grade) or other suitable medium.7.4 Argon, carrier

37、 gas minimum 99.9 % purity.NOTE 2Purification scrubbers to ensure the removal of containmentsare recommended such as moisture (molecular sieve) and hydrocarbontrap filters (activated charcoal or equivalent) are recommended.7.5 Oxygen, combustion gas minimum 99.6 % purity.7.6 Gas Regulators, two-stag

38、e, gas regulators capable ofregulating the pressures to 40 to 60 psi must be used for thecarrier and combustion gases.7.7 Calibration Standards, certified calibration standardsfrom commercial sources or calibration standards prepared inthe laboratory containing the elements of interest at theconcent

39、rations of interest.NOTE 3Other calibration standard sources and diluents may be usedif precision and accuracy are not degraded.NOTE 4Calibration standards are typically re-mixed and re-certifiedon a regular basis depending upon frequency of use and age. Calibrationstandards can have a useful life o

40、f about 6 to 12 months if properly storedin a cool, dark place.NOTE 5A correction for chemical impurity can be used if deemednecessary.7.8 Dibenzothiophene, FW 184.26, 17.399 % S.7.9 Fluorobenzoic Acid, FW 140.11, 13.56 % F.7.10 2,4,5 Trichlorophenol, FW 197.46, 53.87 % Cl.7.11 Hydrogen Peroxide 30

41、%, FW 34.01 H2O2(see Section8 regarding Hazards).7.12 Potassium Hydroxide, for eluent preparation (see Sec-tion 8 regarding Hazards).7.13 Toluene, Xylene, Isooctane or Methanol, Reagentgrade. (Other solvents similar to those occurring in samples tobe analyzed are also acceptable.) Correction for con

42、taminatelevels of elements of interest must be corrected for (solventblank). Alternatively, using a solvent with non-detectablecontamination relative to the sample makes the blank correc-tion unnecessary.7.14 Volumetric Flasks-Type Class A, at the volume speci-fied to use in this method to prepare s

43、tandards, reagents andsolutions.7.15 Stock Standard Solutions of approximately-1000 ug/mLPrepare a stock standard solution by accurately weighingto within 10 % of the target weights for any or all of the targetstandard compound(s) listed in 7.15.1, 7.15.2, and 7.15.3 intoa 100 mL class A volumetric

44、flask. Dilute to volume with theselected solvent described in 7.13. Calculate the actual con-centration of the stock standard solution(s) for each element byusing the equation below with the actual recorded weight of thetarget compound used for each element. This stock standardsolution can be furthe

45、r diluted to other desired concentrations.Other suitable materials, weights and volumes may be substi-tuted in preparing stock calibration standards as long as theperformance of the method is not degraded.Target Standard Compound(s)7.15.1 Fluorobenzoic Acid, (Fluorine), 0.7375 g targetweight.7.15.2

46、2,4,5 Trichlorophenol, (Chlorine), 0.1856 g targetweight.7.15.3 Dibenzothiophene, (Sulfur), 0.5748 g target weight.Calculation FormulaStock Standard Solution g/ml! 5 A!B!106!/C!K! (1)where:A = weight of the target compound actually weighed ingrams, g,B = % concentration of the elements in the respec

47、tive targetcompounds listed in 7.8, 7.9, and 7.10,C = final diluted volume, mL, andK = 100 (factor correction for %).7.16 Phosphate Stock Solution (1.00 mL = 1.00 mgPhosphate)Weigh to within 10 % 1.433 g of potassiumdihydrogen phosphate (KH2PO4) in water and dilute to 1 Lwith water in a class A volu

48、metric flask and mix well.7.17 Absorbing SolutionDilute the Phosphate Stock Solu-tion with water in a class A volumetric flask to a finalconcentration of approximately 1.00 ppm. The concentration of5Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC

49、. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.D7359 133phosphate in the absorbing solutions is used as an internalstandard by the Ion Chromatograph.8. Hazards8.1 Consult the current version of OSHA regulations, sup-pliers Material Safety Data Sheets, and local regulations for allmaterials used in this test method.8.2 High