1、Designation: D 5530 94 (Reapproved 2003)Standard Test Method forTotal Moisture of Hazardous Waste Fuel by Karl FischerTitrimetry1This standard is issued under the fixed designation D 5530; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revi
2、sion, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the determination by KarlFischer (KF) titrimetry of total moisture in solid
3、 or liquidhazardous waste fuels used by industrial furnaces.1.2 This test method has been used successfully on numer-ous samples of hazardous waste fuel composed of solvents,spent oils, paints, and pigments. The expected range ofapplicability for this test method is between 1.0 and 100 %;however, th
4、is evaluation was limited to samples containingapproximately 5 to 50 % water.1.3 The values stated in SI units are to be regarded as thestandard.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 stand
5、ard 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:2D 1193 Specifications for Reagent WaterD 4017 Test Method for Water in Paints and Paint Materialsby Karl Fischer MethodE 691 Pr
6、actice for Conducting an Interlaboratory Study toDetermine the Precision of a Test Method3. Summary of Test Method3.1 An amount of solvent (see 7.3) sufficient to immerse theelectrode in the titration flask fully (see Note 1) is titrated todryness as explained in 9.1, and the Karl Fischer reagent fa
7、ctoris determined by titration of measured amounts of water. Aweighed portion of the sample is dissolved in KF solvent andtitrated with reagent to dryness. If solid material interferes (see5.3) with the electrode or does not dissolve sufficiently, anextraction using KF solvent is performed prior to
8、introductioninto the titration flask. The total moisture in the sample is thendetermined. The final total moisture percent is an average oftwo trials for each sample.3.2 The contents of the tiration flask may be retained andused for additional analyses. The contents of the titration flaskwill need t
9、o be emptied and replaced with new solvent whenthe capacity of the flask is nearly exhausted or when solidmaterial affects the sensing by the electrode.4. Significance and Use4.1 The determination of total moisture is important forassessing the quality of fuels. Water content will affect theheating
10、value of fuels directly and can contribute to instabilityin the operation of an industrial furnace. Additionally, highwater contents can present material handling and storageproblems during winter months or in cold environments.5. Interferences5.1 A small number of oxidants such as ferric and chroma
11、tesalts can oxidize iodide and may produce artificially lowresults.5.2 Certain reductants oxidized by iodine such as mercap-tans, thioacetate, thiosulfate, stannous chloride, sulfides, hyd-roquinone, and phenylenediamines can consume iodine andmay cause artificially high results. Basic materials suc
12、h ashydroxides, oxides, and inorganic carbonates may cause arti-ficially high results by water-forming reactions.5.3 Some types of solid material found in waste-derived fuelmay interfere with the electrode by blocking its contact withthe solvent. Depending on the nature of the solid material,artific
13、ially high or low results can occur.6. Apparatus6.1 Karl Fischer Potentiometric Titration Unit, automatedor semi-automated, equipped with a magnetic vessel stirrer.The user must follow the manufacturers instructions forinstallation and use.NOTE 1The Karl Fischer unit used for developing this test me
14、thodwas equipped with a twin platinum electrode, 25 to 80-mL capacitytitration flask, magnetic stirrer, electronic piston burette, adjustable delayinterval, LED display, visual and audible endpoint notification.6.2 Syringe, 100-L capacity, with needle.1This test method is under the jurisdiction of A
15、STM Committee D34 on WasteManagement and is the direct responsibility of Subcommittee D34.01.06 onAnalytical Methods.Current edition approved April 15, 1994. Published June 1994.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org.
16、For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.6.3 Syringe, 1 to 5-mL capacity, without needle.6.4 Analytical Balan
17、ce, with minimum capacity of 160 gand capable of weighing to 0.0001 g.7. Reagents and Materials7.1 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 Reag
18、ents of the American Chemical Society,where such specifications are available.3Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.7.2 Purity of Water Unless otherwise indicated,
19、 refer-ences to water shall be understood to mean reagent water asdefined by Type II of Specification D 1193.7.3 Karl Fischer SolventThe solvent system must be anon-methanol formulation for the analysis of aldehydes andketones and for general usage. The use of a strictly generalpurpose solvent is no
20、t acceptable because of the potential ofobtaining artificially high results from water-forming reactionsby chemicals with active carbonyl groups.7.4 Karl Fischer ReagentThe reagent should have astandard titer value of 5 mg H2O/mL reagent and be listed asbeing compatible with the solvent system.8. Sa
21、mple8.1 Because stratification or layering of liquid samples ispossible, the laboratory sample should be mixed thoroughly byshaking prior to withdrawing a portion for testing. Stronglymulti-phasic samples should have each layer analyzed sepa-rately and the total moisture percent of the sample calcul
22、ated asa weighted average. Solid samples should be mixed thoroughlyby shaking or stirring, depending on the physical characteris-tics of the sample.9. Calibration and Standardization9.1 Determination of Karl Fischer reagent factor (F):9.1.1 Determine the mg H2O/mL reagent (F) for each newprocurement
23、 of KF solvent and at a minimum of daily on asolvent retained for further titrations (see Section 3).9.1.2 Add a sufficient quantity of solvent to cover theelectrode tip, set the delay interval to 30 s, and engage themagnetic stirrer.9.1.3 Bring the KF solvent to dryness by titrating withreagent to
24、the endpoint. The endpoint is typically indicated bya visual or audible alarm, or both, depending on the equipmentmanufacturer.9.1.4 Refill the burette with reagent.9.1.5 Fill the 100-L syringe with approximately 10 L ofwater and weigh to the nearest 0.0001 g.9.1.6 Dispense the syringe contents into
25、 the titration vesseland replace the sample port stopper immediately. Reweigh thesyringe and record the water mass.9.1.7 Titrate with reagent until the endpoint is reached.Record the titrant volume used.9.1.8 The final value for F should be based on the mean ofa minimum of three replicates.9.1.9 Cal
26、culation:9.1.9.1 Calculate F by the following formula:F mg/mL!5water weight mg!/reagent volume mL! (1)9.1.9.2 The replicate values for F should have a relativestandard deviation of not greater than 5 %. The standardizationshould be repeated if a greater variance is determined.10. Procedure10.1 Bring
27、 the KF solvent to dryness by titrating withreagent to the endpoint. The endpoint is typically indicatedvisually or by an audible alarm, or both, depending on theequipment manufacturer.10.2 Refill the burette with reagent.10.3 Draw a portion of the sample into the 1 to 5-mLsyringe, and clean any res
28、idual sample material from thesyringe tip. If the sample contains a large amount of solids orits viscosity is such that it cannot be drawn into the syringeeasily, it may be necessary to weigh the sample and introduceit using a laboratory spatula or suitable device.10.4 Weigh the syringe with sample
29、to the nearest 0.0001 g.10.5 Add the sample to the titration vessel and allowsufficient time for the material to dissolve adequately. Thesuggested amount of sample based on the amount of expectedwater content is as given in Table 1.NOTE 2The information given in Table 1 is described in Test MethodD
30、4017.10.6 Reweigh the syringe and record the sample mass addedto the vessel to the nearest 0.0001 g.10.7 If solid material is observed interfering with thesensing probe, or it is observed that the sample is not dissolvedin the KF solvent sufficiently, extract the sample with solventas follows:10.7.1
31、 Beginning again with a new sample, combine thesample and solvent gravimetrically at an approximate 1:1 ratioin a large test tube. Record the mass of both sample andsolvent.10.7.2 Cap the sample mixture and shake or mix on avortex-type or orbital mixer for approximately 1 min.10.7.3 Centrifuge the s
32、ample mixture to separate theundissolved/leached solids.10.7.4 Analyze the supernatant beginning with 10.1.3Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, se
33、e 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.TABLE 1 Specimen GuidelinesExpected water, %Approximate SpecimenMass, gApproximate TitrantVolumeat 5 mg/mL tit
34、re, mL0.51.0 5 51013 25 1020310 12 10201030 0.41.0 152570 0.1 20D 5530 94 (2003)210.7.5 In addition to the extracted sample, analyze a blanksolution of virgin KF solvent beginning with 10.1. The KFsolvent blank (mL of titrant used) is subtracted in 10.9.3.10.8 Titrate with reagent until the endpoint
35、 is reached.Record the volume.10.9 The final percentage of water should be based on themean of a minimum of two determinations.10.9.1 Calculation:10.9.1.1 For unextracted samples, calculate the percentagewater as follows:V!F! 5 WW/S! 100 5 water, weight% (2)where:V = reagent volume (mL),F = Karl Fis
36、cher reagent factor (mg/mL),W = mass of water contained in the sample (mg), andS = sample mass (mg).10.9.1.2 For extracted samples, calculate the percentagewater as follows:V solvent blank!F! 5 WW/S!dilution factor! 5 % water (3)where:V = reagent volume (mL),F = Karl Fischer reagent factor (mg/mL),W
37、 = mass of water contained in the sample (mg),S = sample mass (mg), anddilution factor 5KF solvent mg!1 sample mg!sample mg!11. Precision and Bias411.1 PrecisionThe precision estimates are based on aninterlaboratory study in which operators in six different labo-ratories analyzed in duplicate, on se
38、parate days, five samples ofhazardous waste fuel containing between 13 and 32 % water.The results were analyzed statistically in accordance withPractice E 691.11.1.1 Repeatability (Within Laboratory)The coefficientof variation of results (each the average of duplicate determi-nations), obtained by t
39、he same analyst on different days, hasbeen estimated to be 1.3 % relative at 30 degrees of freedom.Therefore, the results of two properly conducted tests, by thesame operator on the same sample, should not differ by morethan 3.6 % of their average.11.1.2 Reproducibility (Between Laboratories)The coe
40、f-ficient of variation of results (each the average of duplicatedeterminations), obtained by analysts in different laboratories,has been estimated to be 4.3 % relative at 5 degrees offreedom. Therefore, the results of properly conducted tests, onidentical samples of the same material, by two differe
41、ntlaboratories, should not differ from each other by more than11.9 % of their average.11.2 BiasThe bias of this test method has not beendetermined because there are no recognized reference stan-dards.12. Keywords12.1 hazardous waste fuel; Karl Fischer titrimetry; percentwater; total moistureASTM Int
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43、y their own responsibility.This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years andif not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standardsand sh
44、ould be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of theresponsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you shouldmake your views known to the ASTM Committee on St
45、andards, at the address shown below.This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org).4A copy of the research report used to develop the precision statement isavailable from ASTM headquarters. Request RR:D 34-1009.D 5530 94 (2003)3
