1、BRITISH STANDARD BS EN 13320:2002 Surface active agents Gas chromatographic trace determination of free ethylene oxide in ethoxylates The European Standard EN 13320:2002 has the status of a British Standard ICS 71.100.40 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBS EN 133
2、20:2002 This British Standard, having been prepared under the direction of the Materials and Chemicals Sector Policy and Strategy Committee, was published under the authority of the Standards Policy and Strategy Committee on 28 March 2002 BSI 28 March 2002 ISBN 0 580 39315 1 National foreword This B
3、ritish Standard is the official English language version of EN 13320:2002. The UK participation in its preparation was entrusted to Technical Committee CII/34, Methods of test for surface active agents, which has the responsibility to: A list of organizations represented on this committee can be obt
4、ained on request to its secretary. Cross-references The British Standards which implement international or European publications referred to in this document may be found in the BSI Standards Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Find”
5、facility of the BSI Standards Electronic Catalogue. A British Standard does not purport to include all the necessary provisions of a contract. Users of British Standards are responsible for their correct application. Compliance with a British Standard does not of itself confer immunity from legal ob
6、ligations. aid enquirers to understand the text; present to the responsible European committee any enquiries on the interpretation, or proposals for change, and keep the UK interests informed; monitor related international and European developments and promulgate them in the UK. Summary of pages Thi
7、s document comprises a front cover, an inside front cover, the EN title page, pages 2 to 12, 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 since publication Amd. No. Date CommentsEUROPEANSTANDAR
8、D NORMEEUROPENNE EUROPISCHENORM EN13320 February2002 ICS71.100.40 Englishversion SurfaceactiveagentsGaschromatographictrace determinationoffreeethyleneoxideinethoxylates AgentsdesurfaceDterminationdetracesdoxyde dthylnelibredanslesthoxylatsparchromatographieen phasegazeuse GrenzflchenaktiveStoffeGas
9、chromatographische SpurenbestimmungvonfreiemEthylenoxidinEthoxylaten ThisEuropeanStandardwasapprovedbyCENon16November2001. CENmembersareboundtocomplywiththeCEN/CENELECInternalRegulationswhichstipulatetheconditionsforgivingthisEurope an Standardthestatusofanationalstandardwithoutanyalteration.Uptodat
10、elistsandbibliographicalreferencesconcernings uchnational standardsmaybeobtainedonapplicationtotheManagementCentreortoanyCENmember. ThisEuropeanStandardexistsinthreeofficialversions(English,French,German).Aversioninanyotherlanguagemadebytra nslation undertheresponsibilityofaCENmemberintoitsownlangua
11、geandnotifiedtotheManagementCentrehasthesamestatusasthe official versions. CENmembersarethenationalstandardsbodiesofAustria,Belgium,CzechRepublic,Denmark,Finland,France,Germany,Greece, Iceland,Ireland,Italy,Luxembourg,Malta,Netherlands,Norway,Portugal,Spain,Sweden,SwitzerlandandUnitedKingdom. EUROPE
12、ANCOMMITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG ManagementCentre:ruedeStassart,36B1050Brussels 2002CEN Allrightsofexploitationinanyformandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.EN13320:2002EEN13320:2002(E) 2 Contents page Foreword3 1 Scope 4 2
13、 Normativereferences 4 3 Principle4 4 Reagents.4 5 Apparatus .4 6 Samplingandpreparationofthetestsample. 5 7 Procedure .5 8 Calculationandexpressionofresults. 7 9 Precision.7 10 Testreport 8 AnnexA (informative) Ringtestresults . .9 AnnexB (informative) Titrationofethyleneoxidestocksolution11EN13320
14、:2002(E) 3 Foreword ThisdocumentEN13320hasbeenpreparedbyTechnicalCommitteeCEN/TC276“Surfaceactiveagents“,the secretariatofwhichisheldbyAFNOR. ThisEuropeanStandardshallbegiventhestatusofanationalstandard,eitherbypublicationofanidenticaltextor byendorsement,atthelatestbyAugust2002,andconflictingnation
15、alstandardsshallbewithdrawnatthelatestby August2002. TheannexesAandBareinformative. AccordingtotheCEN/CENELECInternalRegulations,thenationalstandardsorganizationsofthefollowing countriesareboundtoimplementthisEuropeanStandard:Austria,Belgium,CzechRepublic,Denmark,Finland, France,Germany,Greece,Icela
16、nd,Ireland,Italy,Luxembourg,Malta,Netherlands,Norway,Portugal,Spain, Sweden,SwitzerlandandtheUnitedKingdom.EN13320:2002(E) 4 1Scope ThisEuropeanStandardspecifiesatestmethodforthedeterminationofthecontentoffreeethyleneoxideinthe rangefrom1 mg/kgto100mg/kginpolyglycols,ethoxylatesofalcoholsandalkylphe
17、nolsandinfattyacid polyglycolesters. 2 Normativereferences ThisEuropeanStandardincorporatesbydatedorundatedreference,provisionsfromotherpublications.These normativereferencesarecitedattheappropriateplacesinthetext,andthepublicationsarelistedhereafter.For datedreferences,subsequentamendmentstoorrevis
18、ionsofanyofthesepublicationsapplytothisEuropean Standardonlywhenincorporatedinitbyamendmentorrevision.Forundatedreferencesthelatesteditionofthe publicationreferredtoapplies(includingamendments). ENISO3696, WaterforanalyticallaboratoryuseSpecificationandtestmethods(ISO3696:1987). ISO607, Surfaceactiv
19、eagentsanddetergentsTestmethodsofsampledivision . 3Principle Theethoxylatesare,afteradditionofwater,analyzedbygaschromatographyusingaheadspacesampling accessory.Thefreeethyleneoxidecontentisdeterminedbythestandardadditiontestmethod. 4Reagents Duringtheanalysis,unlessotherwisespecified,useonlyreagent
20、sofrecognizedanalyticalgradeandhavebeen checkedinadvanceastonotinterferewiththeanalyticalresults. 4.1 Watercomplyingwithgrade1asdefinedinENISO3696. 4.2 Ethyleneoxide ,C 2 H 4 O, w(C 2 H 4 O) 99,5%. 4.3 Ethyleneoxide,C 2 H 4 O,dissolvedindichloromethane,vialscontaining50mgofethyleneoxidedissolved in1
21、mlofdichloromethane. 4.4 N,Ndimethylformamide ,C 3 H 7 NO. 5Apparatus Ordinarylaboratoryapparatusandthefollowing. 5.1 Capillarygaschromatograph ,withflameionisationdetector(FID)andheadspacesamplingaccessory.The apparatusshallbeequippedwithasplitsystem.Theheadspacesamplingaccessoryshallbedesignedsuch
22、that eachheadspacebottlecanbethermostatedforadefinedtime. NOTE Sinceethyleneoxideiseasilydecomposedbytracesofimpuritiessuchasacidsandtransitionmetals,(catalysed decomposition),ameticulouslycleansamplingaccessoryisnecessary . 5.2 Fusedsilicacapillarycolumn ,coating:crosslinkeddimethylpolysiloxanes,co
23、lumnlength30m,internal diameter0,25mm,filmthickness1,0 . 5.3 Vials,closablebymeansofaseptum,20ml,suitableforheadspacesamplingaccessory. 5.4 Septumsandaluminiumcaps ,linedwithaluminiumorpolytetrafluoroethylene(PTFE)forclosingthevials.EN13320:2002(E) 5 5.5 Sealingpliers ,forsealingthecapsontothevials.
24、 5.6 Integratororcomputer ,withappropriateevaluationprogramme. 5.7 Analyticalbalance ,accurateto0,1mg. 6 Samplingandpreparationofthetestsample 6.1Sampling ThelaboratorysamplesshallbepreparedandstoredinaccordancewithISO607. 6.2 Testsample NOTE1 Thetestsamplescanbeinliquid,pasteorsolidform . Forpastel
25、ikeproducts,liquefyandhomogenizethelaboratorysamplesbygentlewarming . NOTE2 Ifthetestsampleisheatedabove50C,lowresultswillbeobtained. Donotmeltsolidproductsabove50C . 7Procedure 7.1 Preparationofcalibrationsolutions 7.1.1 Standardsolutions Prepareastocksolutionofethyleneoxide(EO)(4.2)eitherby: a)Dif
26、ference weighing Weigha200mlvolumetricflaskcontainingabout100mlofwater.Passabout500mgofethyleneoxide(4.2)into thewaterandreweigh.Makeupthesolutionto200mlwithwater.Inplaceofdifferenceweighing,theadditionof ethyleneoxide(4.2)canbecarriedoutbyweighinginusingacooledsyringe,or b)Using a vial Dissolvethec
27、ontentsofavialofethyleneoxide(4.3)in250mlofN,Ndimethylformamide(4.4). NOTE AmethodoftitrationoftheethyleneoxidestocksolutionisgiveninannexB. Preparestandardsolutionswithconcentrationsof (C 2 H 4 O)=0,1g/100mland (C 2 H 4 O) = 0,01g/100ml by multistagedilutionswithwaterfromthestocksolution. Storethes
28、tandardsolutionsinarefrigerator. 7.1.2 Calibrationsolutions PreparecalibrationsolutionAasfollows: Place2mlofethyleneoxidestandardsolutionwithaconcentrationof (C 2 H 4 O)=0,01g/100mlina100ml volumetricflaskandmakeuptothemarkwithwater.1mlofthissolutioncontains2 EN13320:2002(E) 6 Preparecalibrationsolu
29、tionBasfollows: Place1mlofethyleneoxidestandardsolutionwithaconcentrationof (C 2 H 4 O)=0,1g/100mlina100ml volumetricflaskandmakeuptothemarkwithwater.1mlofthissolutioncontains10 7.2Determination Weighabout1gofthetestsample(6.2),tothenearest0,1mgintoeachoftwovialsandadd1mlofwaterto each.Closethevials
30、andmakesurethattheyarepressuretight. Weighabout1gofthetestsample(6.2)tothenearest0,1mgintoeachoftwofurthervialsandadd1mlof calibrationsolutionAorBtoeach.Closethevialsandmakesurethattheyarepressuretight. Forproductswithalowdegreeofethoxylation,solubilityproblemscanbeencounteredinpurewater.Inthiscase,
31、 thedeterminationcanbecarriedoutusingadifferentsolventsuchastolueneorN,Ndimethylformamide,provided thatithasbeenshowntogivecomparableresults.Thesolventusedshallbereportedundere)ofthetestreport (seeclause10). Equilibratethesolutionsfor45minat(70 1)C. Injectthesolutionsandperformtheanalysisusingthefol
32、lowinggaschromatographicconditions: temperatureofthetransferline: 150C; thermostatingtemperature: 70C; pressurebuilduptime: 3s; injectiontime: 6s; analysistime: 45min. NOTE 1 GCconditionsdeviatingfromthosegivenabovemaybeusedprovidedthatacorrespondingseparation performanceisdemonstrated. a)Temperatur
33、e oven : 50 Cisothermalfor5min,thenfrom50Cto180Cat5C/min; detector(FID): 250 C. b)Carrier gas helium : about1ml/min; columnpressure: about70kPa(0,7bar); split : about1:40. c) Hydrogenandair OptimizedforFID; d) Evaluation Usinganelectronicintegratororcomputer,withappropriateevaluation programme. NOTE
34、2 Unknownconstituentsofthetestsamplewhichareelutedatthesameretentiontimeasethyleneoxidecancause systematicerrors.Compoundsthatcommonlyoccurinethoxylatessuchasmethanol,ethanol,acetaldehydeand1,4dioxane areseparatedfromethyleneoxideunderthegivenseparationconditions.EN13320:2002(E) 7 8 Calculationandex
35、pressionofresults Theethyleneoxidecontent,w j ,inmicrogramspergramofthetestsample,iscalculatedusingthefollowing equations: m A = A j j 2 1 2 1 = j (1) 2 1 k k k k 2 1 k m C A m B f / ) / ( _ (2) f m A w j j j = (3) where A isthemeanpeakareaofethyleneoxideperunitmassoftheoriginaltestsample,inmillivol
36、tssecondsper gram; A i isthepeakareaofethyleneoxideintheoriginaltestsampleinthej th individualdetermination,inmillivolts seconds; m j isthemassoftheoriginaltestsampleweighedinforthej th individualdetermination,ingrams; j istheindexoftheindividualdetermination; f isthemeanheadspaceresponsefactoroutof
37、twostandardadditions,inmillivoltssecondspermicrogram; B k isthepeakareaofethyleneoxideinthetestsamplewiththek th standardaddition,inmillivoltsseconds; C k isthemassofethyleneoxideaddedtothetestsample,inmicrograms; m k isthemassoftheoriginaltestsampleweighedinforthek th standardaddition,ingrams; k is
38、theindexforthestandardaddition. Calculatetheresultasthemeanof w 1 and w 2 tothenearest0,1 9Precision 9.1 Repeatabilitylimit Theabsolutedifferencebetweentwoindependentsingletestresults,obtainedusingthesamemethodonidentical testmaterialinthesamelaboratorybythesameoperatorusingthesameequipmentwithinash
39、ortintervaloftime, willnotexceedtherepeatabilitylimit, r,inmorethan5%ofcases. TypicalprecisiondataobtainedinaringtestaregiveninannexA. 9.2 Reproducibilitylimit Theabsolutedifferencebetweentwosingletestresults,obtainedusingthesamemethodonidenticaltestmaterial indifferentlaboratoriesbydifferentoperato
40、rsusingdifferentequipment,willnotexceedthereproducibilitylimit, R, inmorethan5%ofcases.EN13320:2002(E) 8 TypicalprecisiondataobtainedinaringtestaregiveninannexA. 10 Testreport Theinformationshallincludethefollowinginformation: a) allinformationnecessaryforthecompleteidentificationofthesample; b) are
41、ferencetothisEuropeanStandard; c) theGCconditionsusedifdeviatingfromthosegivenin7.2; d) theresultscalculatedaccordingtoclause8andthetestmethodchosenforevaluationoftheresults; e) detailsofanyoperationnotspecifiedinthisEuropeanStandardandanyoperationregardedasoptionalas wellasanyincidentslikelytohavea
42、ffectedtheresults.EN13320:2002(E) 9 Annex A (informative) Ringtestresults A.1Ringtests Thedataonrepeatabilityandreproducibilityofthistestmethodaretheresultofaninterlaboratorytestcarriedout asfollowsin1991bytheGermanJointCommitteefortheAnalysisofSurfactants(GAT): testsampleA:alkylphenol 20molesofEO;
43、testsampleB:castoroil 45molesofEO. Eachtestsamplewaspreparedthreetimesaccordingto6.2(testportionofthetestsamplealone+twostandard additions)andanalyzedbygaschromatography. A.2Selectivity Theselectivityofthetestmethodisdefinedastheabilityofthegaschromatographicsystemtodistinguish ethyleneoxidefromotherinterferingcomponents. Thesecondaryconstituentsoccurringinethoxylates,e.g.methanol,ethanol,acetaldehydeand1,4dioxane,canbe separatedfromethyl
