1、Designation: D7359 13D7359 14Standard 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 D73
2、59; 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 reapprov
3、al.1. Scope*1.1 This test method covers the individual determination of total fluorine, chlorine and sulfur in aromatic hydrocarbons and theirmixtures. Samples containing 0.10 to 5010 mg/kg of each element can be analyzed.1.2 This method can be applied to sample typesconcentrations outside the range
4、 of the scope by dilution of the sample in anappropriate solvent to bring the total concentrations of fluorine, chlorine and sulfur within the range covered by the test method.However, it is the responsibility of the analyst to verify the solubility of the sample in the solvent and that the diluted
5、sample resultsconform to the precision and accuracy of the method.1.2.1 Special considerations must be made in order to attain detection limits below 1.0 mg/kg in a sample. The instrument mustbe clean and properly maintained to address potential sources of contamination, or carryover, or both. Multi
6、ple sequentialinjections shall be completed until a stable background is attained. A stable background is considered to be achieved when theanalysis of a minimum of three consecutive system blanks have area counts equal to or less than 5 % RSD for the anions of interest.1.3 In determining the confor
7、mance of the test results using this method to applicable specifications, results shall be roundedoff in accordance with the rounding-off method of Practice E29.1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.1.5 This stan
8、dard 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 appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use. See Section 8.1.5 This standa
9、rd 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 appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use. See Section 9.2. Referenced Doc
10、uments2.1 ASTM Standards:2D1193 Specification for Reagent WaterD3437 Practice for Sampling and Handling Liquid Cyclic ProductsD3505 Test Method for Density or Relative Density of Pure Liquid ChemicalsD6809 Guide for Quality Control and Quality Assurance Procedures for Aromatic Hydrocarbons and Relat
11、ed MaterialsE29 Practice for Using Significant Digits in Test Data to Determine Conformance with SpecificationsE177 Practice for Use of the Terms Precision and Bias in ASTM Test MethodsE288 Specification for Laboratory Glass Volumetric FlasksE691 Practice for Conducting an Interlaboratory Study to D
12、etermine the Precision of a Test Method1 This test method is under the jurisdiction of ASTM Committee D16 on Aromatic Hydrocarbons and Related Chemicals and is the direct responsibility of SubcommitteeD16.04 on Instrumental Analysis.Current edition approved July 15, 2013July 1, 2014. Published Septe
13、mber 2013September 2014. Originally approved in 2008. Last previous edition approved in 20082013as D7359 08.13. DOI: 10.1520/D7359-13.10.1520/D7359-14.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Stan
14、dardsvolume information, refer to the standardsstandards Document Summary page on the ASTM website.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 previous version. Becauseit may not be technically
15、 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 of Changes section appears at the end of this standa
16、rdCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1E969 Specification for Glass Volumetric (Transfer) Pipets2.2 Other Documents:OSHA Regulations, 29 CFR paragraphs 1910.1000 and 1910.1200 33. Terminology3.1 Definitions:3.1.1 combustion
17、 ion chromatography, nan analytical system consisting of pyrohydrolytic combustion followed by ionchromatographic detection.3.1.2 oxidative pyrohydrolytic combustion, na process in which a sample undergoes combustion at temperatures greater than900C in an oxygen rich environment and in the presence
18、of excess water vapor not originating from the combustion of the sample.In oxidative pyrohydrolytic combustion, the sample is pyrolyzed into carbon dioxide, water, hydrogen halides and residual ash;typically elemental oxides.3.1.3 halogens (X), nthe elements fluorine, chlorine, bromine and iodine.3.
19、1.4 hydrogen halide (HX), nare inorganic compounds with the formula HX where X is one of the halogens: fluorine,chlorine, bromine, and iodine. Hydrogen halides are gases that dissolve in water to give acids.3.1.5 sulfur oxide (SOx), nrefers to one or more of the following compounds:3.1.5.1 sulfur di
20、oxide (SO2)3.1.5.2 sulfur trioxide (SO3)3.1.5.3 sulfate (SO4)3.1.6 system blank, na combustion ion chromatography (CIC) analysis with no solvent or sample injection in which the samecombustion, chromatography and time protocols are used as for the sample analysis, but without the combustion of a sam
21、ple orsolvent blank. The system blank must be equal to or less than 50 % (1/2) the area counts of the lowest calibration standard usedfor calibration and a maximum of 50 % (1/2) of the area count of the solvent blank used in the preparation of the calibrationstandards for the anions of interest.3.1.
22、7 solvent blank, na combustion ion chromatography (CIC) analysis of the solvent used for preparation of the calibrationstandards in which the same combustion, chromatography, time protocols and injection volumes are used as for the sampleanalysis. The solvent blank area count must be less than or eq
23、ual to two times (2) the system blank and 50 % (1/2) or less thanthe area counts of the lowest calibration standard used in the calibration of the system for the anions of interest.3.1.8 stock standard solution, nstandard prepared from primary standards and subsequently used to prepare the workingst
24、andard.3.1.9 working standard solution, nstandard prepared from the stock standard solution and subsequently used to prepare thecalibration standards.3.1.10 calibration standard, nstandard prepared from the working standard and subsequently used to calibrate the instrument.3.2 Abbreviations:3.2.1 CI
25、Ccombustion ion chromatography3.2.2 Concconcentration3.2.3 CRMcertified reference material3.2.4 HCIhydrogen choloride3.2.5 HFhydrogen fluoride3.2.6 HXhydrogen halide3.2.7 ICion chromatograph or ion chromatography3.2.8 SOxsulfur oxide (SO2 and SO3)3.2.9 SO2sulfur dioxide3.2.10 SO3sulfur trioxide3.2.1
26、1 SO4sulfate3.2.12 Stdstandard3.2.13 SRMstandard reference material3 Available 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.D7359 1424. Summary of Test Method4.1 Asample of known weight or vol
27、ume is placed into a sample boat and introduced at a controlled rate into a high temperaturecombustion tube. There the sample is combusted in an oxygen rich pyrohydrolytic environment. The gaseous by-products of thecombusted sample are trapped in an absorption medium where the hydrogen halides (HX)
28、formed during combustion disassociateinto their respective ions, X- while the sulfur oxides (SOX) formed are further oxidized to SO42- in the presence of an oxidizingagent. An aliquot of known volume of the adsorbingabsorbing solution is then automatically injected into an ion chromatograph(IC) by m
29、eans of a sample injection valve.The halide and sulfate anions are separated into individual elution bands on the separatoranion separation column of the IC. The conductivity of the eluent is reduced with an anion suppression device prior to the ionchromatographs thermal conductivity detector, where
30、 the anions of interest are measured. Quantification of the fluorine, chlorineand sulfur in the original combusted sample is achieved by first calibrating the system with a series of standards containing knownamounts of fluorine, chlorine and sulfur and then analyzing unknown samples under the same
31、conditions as the standards. Thecombined system of pyrohydrolytic combustion followed by ion chromatographic detection is referred to as Combustion IonChromatography (CIC).5. Significance and Use5.1 The total fluorine, chlorine and sulfur contained in aromatic hydrocarbon matrices can contribute to
32、emissions, be harmfulto many catalytic chemical processes, and lead to corrosion. This test method can be used to determine total sulfur and halogensaromatic hydrocarbon matrices, in finished products andin aromatic hydrocarbons and their mixtures. The results can be used forcompliance determination
33、s when acceptable to a regulatory authority using performance based criteria.6. Interferences6.1 Substances that co-elute with the anions of interest will interfere.Ahigh concentration of one anion can interfere with otherconstituents if their retention times are close enough to affect the resolutio
34、n of their peak.7. Apparatus7.1 Autosampler (Optional), Autosampler, capable of accurately delivering 10 to 80 L of sample into the sample boat. Theautosampler may be used as long as the accuracy and performance of the method is not degraded.a known volume of sample,typically in the range of 10 to 1
35、00 L, into the sample boat.NOTE 1Multiple rinsing The sample syringe should be rinsed with clean solvent between sample injections and/or sampling between different samplevials to minimize carryover contamination from previous samples is recommended.Asolvent flush from a vial separate from the solve
36、nt wash, providingclean, uncontaminated solvent may also be used. These features may be used as long as they do not degrade the performance and accuracy of themethod.followed by a rinse with the next sample when changing from one vial to another. Follow the manufacturers recommendation to minimizeca
37、rryover.7.2 Balance, analytical, with sensitivity to 0.0001 g.7.3 Boat Inlet SystemThe system provides a sampling port for the introduction of liquid and solid samples into the sampleboat and is connected to the inlet of the Pyrohydrolytic Combustion Tube. combustion tube. The system is swept by a h
38、umidifiedinert carrier gas and shall be capable of allowing the quantitative delivery of the material to be analyzed into the pyrohydrolyticoxidation zone at a controlled and repeatable rate.7.4 Boat Inlet Cooler (Optional)CoolerSample volatility and injection volume may require requires an apparatu
39、s capableof cooling the sample boat prior to sample introduction. Thermoelectric coolers (peltier) or recirculating refrigerated liquid devicesare strongly recommended. Switching sample boats between each analysis may prove effective, provided sample size is not toolarge.injection into the boat.7.5
40、Gas Flow ControlThe apparatus must be equipped with flow controllers capable of maintaining a constant supply and flowof oxygen and argon or helium carrier gas.7.6 Furnace FurnaceAn electric furnace which can maintain a minimum temperature of 900C.7.7 Gas AdsorptionAbsorption Unit, having an adsorpt
41、ion tube of either 10 or 20 absorption tube with sufficient capacity to holda minimum of 5 mL which is automatically filled with a known volume of absorption solution by a built-in burette or other similardevice. The Gas Adsorption Unitgas absorption unit is interfaced to the Ion Chromatograph IC an
42、d injects an aliquot of theadsorptionabsorption solution into the Ion Chromatograph IC after the sample is combusted and the by-products of combustionare absorbed. The GasAdsorption Unit rinses out the gas lines with Type I reagent water (gas absorption unit rinses the absorptiontube and7.2) the tra
43、nsfer lines from the pyrohydrolytic combustion tube after the completion of the sample combustion to ensureall the combustion by-products (HX and SO2) are absorbed. The Gas Adsorption Unit rinses the gas lines and adsorption tubecombustion tube to the gas absorption unit with Type I reagent water (7
44、.28.2) or other appropriate absorption solution prior tosample combustion and after the absorption solution is injected into the Ion Chromatograph IC to minimize cross contaminationfrom the previous analysis.contamination.D7359 1437.8 Gas-Tight Sampling Syringe, of 10, 25, 50, 100, or 250- L capacit
45、y and capable of accurately delivering 10 to 80 L ofstandard or sample.microliter quantities.7.9 Pyrohydrolytic Combustion Tube made of quartz and constructed such that when the sample is combusted in the presenceof humidified oxygen, the by-products of combustion are swept into the humidified pyroh
46、ydrolytic combustion zone. The inlet endshall allow for the stepwise introduction and advancement of a sample boat into the heated zone and shall have a side arm for theintroduction of the humidified carrier gas and oxygen. The pyrohydrolytic capable of withstanding temperatures up to 1100C. Thecomb
47、ustion tube must be of ample volume, and have a heated zone with volume and may include quartz wool or other suitablemedium providing sufficient surface area so that the complete pyrohydrolytic to provide sufficient mixing and surface area toensure complete combustion of the sample is ensured.sample
48、.7.10 Humidifier Delivery System, capable of delivering Type 1 reagent water (7.28.2) to the combustion tube at a controlled ratesufficient to provide a pyrohydrolytic environment.7.11 Ion Chromatograph (IC)(IC),4, equipped with:an analytical system with all required accessories including columns,su
49、ppressor and detector.7.11.1 Injection System, High Performance inert PEEK-(polyetheretherketone) flow path system is required.capable ofdelivering 20 to 500 L with a precision better than 1 % or as recommended for this determination by the manufacturer. Largervolumes can be used as long as the performance criteria of the method are not degraded.7.11.2 Pumping System, High Pressure eluent pump, capable of delivering 0.0 to 5 mL/min (without eluent generator; 0.1 to 3mL/min (with eluent generator), in 0.01 mL/min increments. Flow rate acc
