1、DRAFT FOR DEVELOPMENT DD CEN/TS 14494:2003 Leather Chemical tests Determination of the content of pentachlorophenol in leather ICS 59.140.30 Copyright European Committee for Standardization Provided by IHS under license with CEN Not for Resale No reproduction or networking permitted without license
2、from IHS - - -DD CEN/TS 14494:2003 This Draft for Development was published under the authority of the Standards Policy and Strategy Committee on 10 April 2003 BSI 10 April 2003 ISBN 0 580 41534 1 National foreword This Draft for Development is the English language version of CEN/TS 14494:2003. This
3、 publication is not to be regarded as a British Standard. It is being issued in the Draft for Development series of publications and is of a provisional nature because there is a need for users to establish some experience with the method. It should be applied on this provisional basis, so that info
4、rmation and experience of its practical application may be obtained. Comments arising from the use of this Draft for Development are requested so that UK experience can be reported to the European organization responsible for its conversion to a European standard. A review of this publication will b
5、e initiated 2 years after its publication by the European organization so that a decision can be taken on its status at the end of its 3-year life. Notification of the start of the review period will be made in an announcement in the appropriate issue of Update Standards. According to the replies re
6、ceived by the end of the review period, the responsible BSI Committee will decide whether to support the conversion into a European standard, to extend the life of the Technical Specification or to withdraw it. Comments should be sent in writing to the Secretary of BSI Technical Committee TCI/69, Le
7、ather and footwear, at British Standards House, 389 Chiswick High Road, London W4 4AL, giving the document reference and clause number and proposing, where possible, an appropriate revision of the text. A list of organizations represented on this committee can be obtained on request to its secretary
8、. Cross-references The British Standards which implement international or European publications referred to in this document may be found in the BSI Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Electronic Catalogue
9、or of British Standards Online. Summary of pages This document comprises a front cover, an inside front cover, the CEN/TS title page, pages 2 to 8, an inside back cover and a back cover. The BSI copyright date displayed in this document indicates when the document was last issued. Amendments issued
10、since publication Amd. No. Date Comments Copyright European Committee for Standardization Provided by IHS under license with CEN Not for Resale No reproduction or networking permitted without license from IHS - - -TECHNICALSPECIFICATION SPCIFICATIONTECHNIQUE TECHNISCHESPEZIFIKATION CEN/TS14494 March
11、2003 ICS59.140.30 Englishversion LeatherChemicaltestsDeterminationofthecontentof pentachlorophenolinleather ThisTechnicalSpecification(CEN/TS)wasapprovedbyCENon27October2002forprovisionalapplication. TheperiodofvalidityofthisCEN/TSislimitedinitiallytothreeyears.AftertwoyearsthemembersofCENwillberequ
12、ested tosubmittheir comments,particularlyonthequestionwhethertheCEN/TScanbeconvertedintoaEuropeanStandard. CENmembersarerequiredtoannouncetheexistenceofthisCEN/TSinthesamewayasforanENandtomaketheCEN/TSavailable .It ispermiss bletokeepconflictingnationalstandardsinforce(inparalleltotheCEN/TS)untilthe
13、finaldecisionaboutthep ossible conversionoftheCEN/TSintoanENisreached. CENmembersarethenationalstandardsbodiesofAustria,Belgium,CzechRepublic,Denmark,Finland,France,Germany,Greece, Hungary,Iceland,Ireland,Italy,Luxembourg,Malta,Netherlands,Norway,Portugal,Slovakia,Spain,Sweden,SwitzerlandandUn ited
14、Kingdom. EUROPEANCOMMITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG ManagementCentre:ruedeStassart,36B1050Brussels 2003CEN Allrightsofexploitationinanyformandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.CEN/TS14494:2003E Copyright European Committee for
15、Standardization Provided by IHS under license with CEN Not for Resale No reproduction or networking permitted without license from IHS CEN/TS14494:2003(E) Contents 1 Scope 4 2 Normativereferences . 4 3 Principle . 4 4 Definitions 4 5 Apparatusandauxiliarydevices . 4 6 Chemicals 5 7 Samplingandprepar
16、ationofsamples. . 5 8 Procedures. 5 9 Expressionofresults. . 7 10 Testreport 7 AnnexA (informative) Reliabilityofthemethod. .8 Copyright European Committee for Standardization Provided by IHS under license with CEN Not for Resale No reproduction or networking permitted without license from IHS - - -
17、CEN/TS14494:2003(E) 3 Foreword Thisdocument(CEN/TS14494:2003)hasbeenpreparedbyCEN/TC289,“Leather“theSecretariatofwhichis heldbyUNI. ItisbasedontheEnglishtranslationof DIN53313Draft1999 anddescribesaprocedurewherePCPisacetylated beforethechromatographicdetectionandtheamountofthedetectedPCPacetateisqu
18、antifiedviaaninternal standardcorrection. AccordingtotheCEN/CENELECInternalRegulations,thenationalstandardsorganizationsofthefollowing countriesareboundtoanouncethisEuropeanStandard:Austria,Belgium,CzechRepublic,Denmark,Finland, France,Germany,Greece,Hungary,Iceland,Ireland,Italy,Luxembourg,Malta,Ne
19、therlands,Norway,Portugal, SlovakRepublic,Spain,Sweden,SwitzerlandandtheUnitedKingdom. AnnexAisinformative. Copyright European Committee for Standardization Provided by IHS under license with CEN Not for Resale No reproduction or networking permitted without license from IHS CEN/TS14494:2003(E) 1Sco
20、pe ThisTechnicalSpecificationspecifiesamethodfordeterminingthecontentofpentachlorophenol(PCP),itssalts andestersinleather. 2 Normativereferences ThisTechnicalSpecificationincorporatesbydatedorundatedreference,provisionsfromotherpublications.These normativereferencesarecitedattheappropriateplacesinth
21、etextandthepublicationsarelistedhereafter.For datedreferences,subsequentamendmentstoorrevisionsofanyofthesepublicationsapplytothisTechnical Specificationonlywhenincorporatedinitbyamendmentorrevision.Forundatedreferencesthelatesteditionof thepublicationreferredtoapplies(includingamendments). ENISO369
22、6:1995,WaterforanalyticallaboratoryuseSpecificationandtestmethods(ISO3696:1987) ENISO4044,LeatherPreparationofchemicaltestsamples(ISO4044:1998) ENISO2418,LeatherChemical,physicalandmechanicalandfastnesstestsSamplinglocation (ISO2418:2002) ENISO2419,LeatherPhysicalandmechanicaltestsSamplepreparationa
23、ndconditioning(ISO2419:2002) 3Principle Firstofalltheleatherissubmittedtosteamdistillation. Afterextractioninto nhexanethePCPisacetylatedbyaceticanhydrideandthePCPacetatesanalysedbygas chromatographywithanECDdetector.Quantificationisperformedbyanexternalstandardandcorrectionmade withaninternalstanda
24、rd. 4Definitions Theconcentrationofpentachlorophenolcanconsistoffreepentachlorophenol,itssaltsandesters.PCPis detectedgaschromatographicallyasitsderivative,PCPacetate.ThePCPcontentisgiveninmg/kgsample. 5 Apparatusandauxiliarydevices 5.1 GaschromatographwithECDorMSD 5.2 Analyticalbalanceweightingtoan
25、accuracyof0,1mg 5.3 Suitableapparatusdesignedforsteamdistillation 5.4 Shakingmachine 5.5 Volumetricflasks500ml,50ml 5.6 Erlenmeyerflask100ml 5.7 Separatingfunnel250ml 5.8 Pasteurpipette,graduatedpipette,suitableautopipette Copyright European Committee for Standardization Provided by IHS under licens
26、e with CEN Not for Resale No reproduction or networking permitted without license from IHS - - -CEN/TS14494:2003(E) 5 6Chemicals Unlessotherwisespecified,analyticalgradechemicalsshouldbeused.Watermustbedistilledordeionised,Grade 3inaccordancewithENISO3696:1995. 6.1Stocksolutions 6.1.1 Pentachlorophe
27、nol,100g/mlinacetone 6.1.2 PCPacetate10g/mlin nhexane 6.1.3 PCPacetateStandard0,04mg/lPCPacetate(correspondsto0,0346mgPCP/l)in nhexane 6.1.4 TetrachloroguajacolTCG(Tetrachloromethoxyphenol)100g/mlinacetone,markerandinternalstandard, meltingpoint118C119C 6.2Sulphuricacid,1M 6.3nhexaneforresidueanalys
28、is 6.4Potassiumcarbonate,K 2 CO 3 6.5Aceticanhydride,C 4 H 6 O 3 6.6Molecularsieve1020meshbeads,porediameter0,3nm.Oranhydroussodiumsulphate 6.7DistilledwaterinaccordancewithGrade3ofENISO3696:1995. 6.8Triethylamine 6.9Acetone 7 Samplingandpreparationofsamples IfpossiblesampleinaccordancewithENISO2418
29、andgrindleatherinaccordancewithENISO4044.Ifsampling inaccordancewithENISO2418isnotpossible(e.g.leathersfromfinishedproductslikeshoes,garments)details aboutsamplinghavetobegiveninthetestreport. ConditionthegroundtestsampleinaccordancewithENISO2419priortoweighing. 8Procedures 8.1Steamdistillation Appr
30、oximately1,0goftheleathersampleisweighedaccuratelyintothedistillationvessel(5.3)and20ml1M sulphuricacid(6.2)and0,1mlTCGstocksolution(6.1.4)areadded.Thecontentofthevesselissubmittedtoa steamdistillationbyusingasuitablesteamdistillationapparatus.A500mlvolumetricflask(5.5)with5gK 2 CO 3 (6.4)isusedasar
31、eceiver. About450mlaredistilled.Makeuptovolumewithwater. Inthecaseofextremefoamingtheheatsourceshouldbereduced. Copyright European Committee for Standardization Provided by IHS under license with CEN Not for Resale No reproduction or networking permitted without license from IHS - - -CEN/TS14494:200
32、3(E) 8.2LiquidLiquidExtractionandacetylation 100mlofthedistillateobtainedin8.1istransferredintoa250mlseparatingfunnel(5.7). 20ml nhexane(6.3)and1,5mlaceticanhydride(6.5)and0,5mltriethylamine(6.8)areaddedtothesolutionand shakenfor30minutesvigorouslyonamechanicalshaker(seeNOTE). Afterphaseseparationth
33、eorganiclayeristransferredtoa100mlconicalflask(5.6)andtheaqueouslayeris shakenagainwith20ml nhexane. Thecombined nhexaneextractsaredehydrated,witheithermolecularsievesoranhydroussodiumsulphate(6.6) ina100mlconicalflask(5.6)forabout10min. Afterwardsthe nhexaneextractisdecantedquantitativelyunderwashi
34、ngwith nhexaneintoa50mlvolumetric flask(5.5). Itismadeuptovolumewith nhexane. ThissolutionisanalysedbyGC(5.1). NOTE Thederivatisationstepisatwophasereactionanddependsverystronglyontheintensityofshaking.Usea suitablemechanicalshakerwithahighshakingfrequency.Donottrytoshakebyhandbecausethiswillproduce
35、incorrect results. 8.3PreparationofcalibrationmixtureforacetylatedPCPandTCG 8.3.1 DerivatisationofPCPandTCGStandardforrecoveryrate Tocalculatetherecovery,aPCP/TCGstandardmixtureispreparedlikethesample. Therefore100lofstocksolution(6.1.1)and100lTCG(6.1.4)ismeasuredintothedistillationvesseltogether wi
36、th20mlsulphuricacid(6.2).Thissolutionistreatedinthesamewayasthesample. NOTE Therecoveryrateshallbehigherthan90%. 8.3.2 PCPacetateStandard(Externalstandard) InadditionaPCPacetateStandard(6.1.3)isanalyseddirectlybygaschromatography.Thefinalconcentrationfor theGCis0,04mg/lPCPacetate. Thisstandardisincl
37、udedinthecalculation. 8.3.3 DerivatisationofTCGStandard 20loftheTCGsolution(6.1.4)areacetylatedin30mlof0,1M/lK 2 CO 3 inthesamewayasthesample andthe organiclayeristransferredintoa50mlvolumetricflask(5.5). ATCGStandardisanalysedinthesamewayasthesample. 8.4CapillaryGasChromatography(GC) Thedescribedch
38、romatographicconditionsareonlyexamples. Capillarycolumn: fusedquartz,(mediumpolarity)e.g.95%dimethyl5%diphenylpolysiloxane, length50m,innerdiameter:0,32mm,filmthickness:0,25m Detector/detectortemperature: ECD/280C Injectionsystem: split/splitless60seconds Injectionvolume: 2l Copyright European Commi
39、ttee for Standardization Provided by IHS under license with CEN Not for Resale No reproduction or networking permitted without license from IHS - - -CEN/TS14494:2003(E) 7 Injectortemperature: 250C Carriergas: Helium Makeupgas: Argon(95%)/Methane(5%) TemperatureProgramme: 80C(1min) 6C/min 280C(10min)
40、 Expressionofresults Theareasofthesinglepeakswillbecomparedwiththeareasofthestandardwhichareanalysedatthesametime andcalculated. ThePCPconcentrationiscalculatedasamassportionMinmg/kgleathersampleaccordingtothefollowing equation: E A F V C A M PCPSt TCG PCPSt PCP PCP = b Sample A n calibratio A F TCG
41、 TCG TCG = A = Peakarea C = ConcentrationPCPStandardg/ml(6.1.3)(0,04mgPCPacetateisequivalentto0,0346mgfreePCP) E = Weightofsampleing V = finalsamplevolumeinml = Dilutionrate F = FactorinternalStandard(TCG) Indices:PCPSt= PentachlorophenolStandard TCG: InternalStandard 10 Testreport Thetestreportshal
42、lincludethefollowing: a) referencetothisTechnicalSpecification; b) type,originanddesignationoftheanalysedleathersampleandthesamplingmethodused; c) theanalyticalresultforPCPcontentinmg/kgroundedtoonedecimalplace; d) anydeviationsfromtheanalyticalprocedure; e) dateofthetest. Copyright European Committ
43、ee for Standardization Provided by IHS under license with CEN Not for Resale No reproduction or networking permitted without license from IHS - - -CEN/TS14494:2003(E) Annex A (informative) Reliabilityofthemethod QuantificationlimitofPCP: 0,1mg/kg RecoveryofPCP: 96107% (0,09ppm3ppm) RecoveryofPCPAcet
44、ateStandard: 80% ThequantificationofTriandTetrachlorophenolispossible. Themethodhasbeentestedinaninterlaboratorytrialwith3differentleathers.(A,BandC). Leather Meaninmg/kg S r inmg/kg rinmg/kg s R inmg/kg Rinmg/kg A 6.7 0.2 1.2 0.7 2.3 B 16.8 0.2 1.4 4.4 5.8 C 5.0 0.1 0.9 0.3 1.5 S r = Standarddeviationofrepeatability r = repeatability S R = Standarddeviationofreproducibility R = reproducibility Cop
