1、Designation: D5808 09a (Reapproved 2014)Standard Test Method forDetermining Chloride in Aromatic Hydrocarbons andRelated Chemicals by Microcoulometry1This standard is issued under the fixed designation D5808; the number immediately following the designation indicates the year oforiginal adoption or,
2、 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. Scope1.1 This test method covers the organic chlorides in aro-matic hydrocarbons, their d
3、erivatives, and related chemicals.1.2 This test method is applicable to samples with chlorideconcentrations from 1 to 25 mg/kg.1.3 This test method is preferred over Test Method D5194for products, such as styrene, that are polymerized by thesodium biphenyl reagent.1.4 In determining the conformance
4、of the test results usingthis method to applicable specifications, results shall berounded off in accordance with the rounding-off method ofPractice E29.1.5 Organic chloride values of samples containing inorganicchlorides will be biased high due to partial recovery ofinorganic species during combust
5、ion. Interference from inor-ganic species can be reduced by water washing the samplebefore analysis. This does not apply to water soluble samples.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 pur
6、port 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. For specific hazardstatements, see 7.3 and S
7、ection 9.2. Referenced Documents2.1 ASTM Standards:2D1193 Specification for Reagent WaterD1555M Test Method for Calculation of Volume and Weightof Industrial Aromatic Hydrocarbons and CyclohexaneMetricD3437 Practice for Sampling and Handling Liquid CyclicProductsD5194 Test Method for Trace Chloride
8、in Liquid AromaticHydrocarbonsD6809 Guide for Quality Control and Quality AssuranceProcedures for Aromatic Hydrocarbons and Related Ma-terialsE29 Practice for Using Significant Digits in Test Data toDetermine Conformance with SpecificationsE691 Practice for Conducting an Interlaboratory Study toDete
9、rmine the Precision of a Test Method2.2 Other Document:OSHA Regulations, 29CFR paragraphs 1910.1000 and1910.120033. Terminology3.1 Definitions:3.1.1 dehydration tube, nchamber containing concen-trated sulfuric acid that scrubs the effluent gases from combus-tion to remove water vapor.3.1.2 oxidative
10、 pyrolysis, na process in which a sample iscombusted in an oxygen-rich atmosphere at high temperatureto break down the components of the sample into elementaloxides.3.1.3 recovery factor, nan indication of the efficiency ofthe measurement computed by dividing the measured value ofa standard by its t
11、heoretical value.3.1.4 reference sensor pair, ndetects changes in silver ionconcentration.3.1.5 test titration, na process that allows the coulometerto set the endpoint and gain values to be used for sampleanalysis.3.1.6 titration parameters, nvarious instrumental condi-tions that can be changed for
12、 different types of analysis.1This test method is under the jurisdiction of ASTM Committee D16 onAromatic Hydrocarbons and Related Chemicals is the direct responsibility ofSubcommittee D16.04 on Instrumental Analysis.Current edition approved Feb. 1, 2014. Published February 2014. Originallyapproved
13、in 1995. Last previous edition approved in 2009 as D5808 09a. DOI:10.1520/D5808-09AR14.2For 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 Summar
14、y 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 standardCopyright ASTM International, 100 Barr Harbor
15、Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States13.1.7 working electrode (generator electrode), nan elec-trode consisting of an anode and a cathode separated by a saltbridge; maintains a constant silver ion concentration.4. Summary of Test Method4.1 A liquid specimen is injected i
16、nto a combustion tubemaintained at 900C having a flowing stream of oxygen andargon carrier gas. Oxidative pyrolysis converts the organichalides to hydrogen halides that then flow into a titration cellwhere it reacts with silver ions present in the electrolyte. Thesilver ion thus consumed is coulomet
17、rically replaced and thetotal electrical work to replace it is a measure of the organichalides in the specimen injected (see Annex A1).5. Significance and Use5.1 Organic as well as inorganic chlorine compounds canprove harmful to equipment and reactions in processes involv-ing hydrocarbons.5.2 Maxim
18、um chloride levels are often specified for processstreams and for hydrocarbon products.5.3 Organic chloride species are potentially damaging torefinery processes. Hydrochloric acid can be produced inhydrotreating or reforming reactors and this acid accumulatesin condensing regions of the refinery.6.
19、 Interferences6.1 Both nitrogen and sulfur interfere at concentrationsgreater than approximately 0.1 %.NOTE 1To ensure reliable detectability, all sources of chloridecontamination must be eliminated.6.2 Bromides and iodides, if present, will be calculated aschlorides. However, fluorides are not dete
20、cted by this testmethod.6.3 Organic chloride values of samples containing inorganicchlorides will be biased high due to partial recovery ofinorganic species during combustion. Interference from inor-ganic species can be reduced by water washing the samplebefore analysis. This does not apply to water
21、 soluble samples.7. Apparatus7.1 Pyrolysis Furnace, which can maintain a temperaturesufficient to pyrolyze the organic matrix and convert allchlorine present in the sample to hydrogen chloride.7.2 Pyrolysis Tube, made of quartz and constructed so thatwhen a sample is volatilized in the front of the
22、furnace, it isswept into the pyrolysis zone by an inert gas, where itcombusts when in the presence of oxygen. The inlet end of thetube must have a sample inlet port with a septum throughwhich the sample can be injected by syringe. The inlet endmust also have side arms for the introduction of oxygen
23、andinert carrier gas. The pyrolysis tube must be of ample volume,so that complete pyrolysis of the sample is ensured.7.3 Titration Cell, containing a reference and sensor pair ofelectrodes and a generator anode/cathode pair of electrodes tomaintain constant chloride ion concentration. An inlet from
24、thepyrolysis tube and magnetic stirring is also required.(WarningExcessive stirring speed will decouple the stirringbar and cause it to rise in the titration cell and possibly damagethe electrodes. A slight vortex in the cell will be adequate.)7.4 Microcoulometer, capable of measuring the potential
25、ofthe sensing-reference electrode pair, and comparing this poten-tial with a bias potential, and amplifying the difference to theworking electrode pair to generate a current. The microcou-lometer output voltage signal should be proportional to thegenerating current.7.5 Automatic Boat Drive, having v
26、ariable stops, such thatthe sample boat may be driven into the furnace, and stopped atvarious points as it enters the furnace.7.6 Controller, with connections for the reference, working,and sensor electrodes. The controller is used for setting ofoperating parameters and integration of data.7.7 Dehyd
27、ration Tube, positioned at the end of the pyrolysistube so that effluent gases are bubbled through a sulfuric acidsolution, and water vapor is subsequently trapped, while allother gases are allowed to flow into the titration cell.7.8 Gas-Tight Sampling Syringe, having a 50 l capacity,capable of accu
28、rately delivering 10 to 40 l of sample.7.9 Quartz Boats.8. Reagents and Materials8.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the Am
29、erican Chemical Society,where such specifications are available.4Other grades may beused, provided that the reagent is of sufficiently high purity topermit its use without lessening the accuracy of the determi-nation.8.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understo
30、od to mean reagent water conformingto Specification D1193, Type II or III.8.3 Acetic AcidGlacial acetic acid (CH3COOH).8.4 Argon or Helium, 99.9 % minimum purity required ascarrier gas.8.5 Amidosulfonic Acid (H2NSO3H), minimum purity 99.3-100.3 %.8.6 Sodium Acetate, anhydrous, (NaCH3CO2), fine granu
31、lar.8.7 Cell Electrolyte SolutionDissolve 1.35 g sodium ac-etate (NaCH3CO2) in 850 mL of acetic acid (CH3COOH), anddilute to 1000 mL with water or follow manufacturersrecommendations.NOTE 2Bulk quantities of the electrolyte should be stored in a darkbottle or in a dark place and be prepared fresh at
32、 least every two weeks.4Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. 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 U
33、nited States Pharmacopeiaand National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,MD.D5808 09a (2014)28.8 Oxygen, 99.6 % minimum purity is required as thereactant gas.8.9 Gas Regulators, two-stage gas regulators must be usedfor the reactant and carrier gas.8.10 Potassium Nitrat
34、e (KNO3), fine granular.8.11 Potassium Chloride (KCl), fine granular.8.12 Potassium Sulfate (K2SO4), crystalline.8.13 Working Electrode Solution (10 % KNO3)Dissolve50 g potassium nitrate (KNO3) in 500 mL of distilled water.8.14 Inner Chamber Reference Electrode Solution (1 MKCl)Dissolve 7.46 g potas
35、sium chloride (KCl) in 100 mL ofdistilled water.8.15 Outer Chamber Reference Electrode Solution (1 MKNO3)Dissolve 10.1 g potassium nitrate (KNO3) in 100 mLof distilled water.8.16 Sodium Chloride (NaCl), fine granular.8.17 Sodium Perchlorate (NaClO4), crystalline.8.18 Sulfuric Acid, (sp gr 1.84), (H2
36、SO4) concentrated.8.19 2,4,6-Trichlorophenol (TCP) (C6H3OCl3), fine granu-lar.8.20 SolventThe solvent of choice should be capable ofdissolving the chloride sample. The solvent of choice shouldhave a boiling point similar to the sample being analyzed.Suggested possibilities include, but not limited t
37、o, methanol,isooctane, toluene, and p-xylene.8.21 Chloride Standard Stock SolutionWeigh accurately0.093 g of 2,4,6-Trichlorophenol to 0.1 mg. Transfer to a500-mL volumetric flask. Dilute to the mark with methanol.gCl/mL MeOH 5 grams of TCP! 3 %Cl in TCP!3106/500 mL MeOH (1)where:TCP = 2,4,6, Trichlo
38、rophenolMeOH = Methanol%Cl in TCP = 53.869. Hazards9.1 Consult the current version OSHA regulations, suppli-ers Material Safety Data Sheets, and local regulations for allmaterials used in this test method.10. Sampling10.1 Consult guidelines for taking samples from bulk inaccordance with Practice D34
39、37.11. Preparation of Apparatus11.1 Install the instrument in accordance with manufactur-ers instructions.11.2 Adjust gas flows and pyrolysis temperature(s) to theoperating conditions as recommended by the manufacturer.11.3 The actual operation of injecting a sample will varydepending upon the instr
40、ument manufacturer and the type ofinlet system used.11.4 Prebake the sample boats to be used for the determi-nation.12. Calibration and Standardization12.1 Using the chloride standard stock solution (see 8.21),make a series of three calibration standards covering the rangeof expected chloride concen
41、tration.12.2 Into three 100-mL volumetric flasks, respectively pipet1, 15, and 30 mL of chloride stock solution and dilute to themark with solvent. (The standards are approximately 1 mgCl/mL, 15 mg Cl/mL H and 30 mg Cl/mL.)12.3 It is customary to use a one-point calibration, but ifanalyzing a wide r
42、ange of samples, use a three-point calibra-tion.12.4 The sample size can be determined eithervolumetrically, by syringe, or by mass. Make sure that thesample size is 80 % or less of the syringe capacity.12.4.1 Volumetric measurement can be utilized by filling thesyringe with standard, carefully elim
43、inating all bubbles, andpushing the plunger to a calibrated mark on the syringe, andrecording the volume of liquid in the syringe. After injectingthe standard, read the volume remaining in the syringe. Thedifference between the two volume readings is the volume ofstandard injected. This test method
44、requires the known ormeasured density, to the third decimal place. Densities can befound in Test Method D1555M.12.4.2 Alternatively, the syringe may be weighed before andafter the injection to determine the weight of sample injected.This technique provides greater precision than the volumedelivery m
45、ethod, provided a balance with a precision of60.0001 g is used.12.5 Follow the instrument manufacturers recommendationfor introducing samples into the instrument.12.6 Repeat the measurement of each calibration standard atleast three times.12.7 If the calibration standards come out high or low,prepar
46、e fresh standards. If the calibration standards remainhigh or low, follow the instrument manufacturers recommen-dations to correct.12.8 Construct a three-point curve using the instrumentmanufacturers recommendations.13. Procedure13.1 Clean the syringe to be used for the sample. Flush itseveral times
47、 with the sample. Determine the chloride concen-tration in accordance with 12.4 12.6.13.2 Chloride determination for the sample may require achange in titration parameters or adjustment in sample size, orboth.14. Calculation14.1 Calculate results utilizing volume and known specificgravity in milligr
48、ams per kilograms as follows:Chloride, mg/kg 5M 2 B!V 3D31RF(2)D5808 09a (2014)314.2 Calculate results utilizing weight of sample, consider-ing dilutions in milligrams per kilograms as follows:Chloride, mg/kg 5M 2 B!w31RF(3)where:M = measured chloride value, gB = blank chloride value, gV = sample in
49、jection volume, mLw = weight of sample, gD = densityRF = recovery factor =grams chlorides titratedtheoretical value14.3 If this equation does not apply to your instrument, thenfollow instrument manufacturers recommendations.15. Report15.1 Report the chloride results as mg/kg.16. Precision and Bias516.1 PrecisionThe results from six laboratories were usedto generate statistical data. Three values were recorded for eachsample. The standard used to calibrate a standard curve wasprovided with the samples and a volume of 40 L was specifiedfo
