1、BRITISH STANDARD BS EN 13466-1:2001 Fertilizers Determination of water content (Karl Fischer methods) Part 1: Methanol as extracting medium The European Standard EN 13466-1:2001 has the status of a British Standard ICS 65.080 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBS E
2、N 13466-1:2001 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 10 April 2002 BSI 10 April 2002 ISBN 0 580 39472 7 National foreword
3、 This British Standard is the official English language version of EN 13466-1:2001. The UK participation in its preparation was entrusted to Technical Committee CII/37, Fertilizers and related chemicals, which has the responsibility to: A list of organizations represented on this committee can be ob
4、tained 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 o
6、bligations. 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 Th
7、is document comprises a front cover, an inside front cover, the EN title page, pages 2 to 10, 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 CommentsEUROPEANSTANDA
8、RD NORMEEUROPENNE EUROPISCHENORM EN134661 October2001 ICS65.080 Englishversion FertilizersDeterminationofwatercontent(KarlFischer methods)Part1:Methanolasextractingmedium EngraisDterminationdelateneureneau(MthodesKarl Fischer)Partie1:Lemthanolcommemilieudextraction DngemittelBestimmungdesWassergehal
9、tes(Karl FischerVerfahren)Teil1:MethanolalsExtraktionsmittel ThisEuropeanStandardwasapprovedbyCENon18August2001. CENmembersareboundtocomplywiththeCEN/CENELECInternalRegulationswhichstipulatetheconditionsforgivingthisEurope an Standardthestatusofanationalstandardwithoutanyalteration.Uptodatelistsandb
10、ibliographicalreferencesconcernings uchnational standardsmaybeobtainedonapplicationtotheManagementCentreortoanyCENmember. ThisEuropeanStandardexistsinthreeofficialversions(English,French,German).Aversioninanyotherlanguagemadebytra nslation undertheresponsibilityofaCENmemberintoitsownlanguageandnotif
11、iedtotheManagementCentrehasthesamestatusasthe official versions. CENmembersarethenationalstandardsbodiesofAustria,Belgium,CzechRepublic,Denmark,Finland,France,Germany,Greece, Iceland,Ireland,Italy,Luxembourg,Netherlands,Norway,Portugal,Spain,Sweden,SwitzerlandandUnitedKingdom. EUROPEANCOMMITTEEFORST
12、ANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG ManagementCentre:ruedeStassart,36B1050Brussels 2001CEN Allrightsofexploitationinanyformandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.EN134661:2001EEN134661:2001(E) 2 Contents page Foreword3 Introduction .4 1 Scope 5
13、 2 Normativereferences 5 3 Principle5 4 Reagents.5 5 Apparatus .5 6 InstallationandtestoftheKarlFischertitrator 6 7 Sampling.6 8 Procedure .6 9 Calculationandexpressionofresults. 8 10 Precision.9 11 Testreport 9 Bibliography 10EN134661:2001(E) 3 Foreword ThisEuropeanStandardhasbeenpreparedbyTechnica
14、lCommitteeCEN/TC260“Fertilizersandliming materials“,thesecretariatofwhichisheldbyDIN. ThisEuropeanStandardshallbegiventhestatusofanationalstandard,eitherbypublicationofanidenticaltextor byendorsement,atthelatestbyApril2002,andconflictingnationalstandardsshallbewithdrawnatthelatestby April2002. Accor
15、dingtotheCEN/CENELECInternalRegulations,thenationalstandardsorganizationsofthefollowing countriesareboundtoimplementthisEuropeanStandard:Austria,Belgium,CzechRepublic,Denmark,Finland, France,Germany,Greece,Iceland,Ireland,Italy,Luxembourg,Netherlands,Norway,Portugal,Spain,Sweden, SwitzerlandandtheUn
16、itedKingdom.EN134661:2001(E) 4 Introduction Thewatercontentoffertilizershasasignificanteffectontheirqualityand,especially,theirstorageandhandling properties. Watercanbepresentinanumberofformssuchasfreewater,boundwaterandwaterofcrystallization.Itisoften importanttobeabletodistinguishbetweentheseforms
17、ofwater.Thegravimetricmethodsfordeterminationof waterstandardizedinEN12048andEN12049haveonlylimitedapplicability. TheKarlFischermethodisapplicabletoawiderangeoffertilizers.However,thereareseveralvariationstothe basictechnique,differentformulationsoftheKarlFischerreagentsarecommerciallyavailableandan
18、umberof differentsolventscanbeused.Inthisstandard,methanoland2propanolareusedasextractingmediato distinguishbetweenthedifferentformsofwaterpresentinfertilizers. EN13466“FertilizersDeterminationofwatercontent(KarlFischermethods)“consistsoftwoparts: Part1:Methanolasextractingmedium Part2:2propanolasex
19、tractingmedium Asexamplesofthedifferencebetweenmethanoland2propanolasextractingmediamethanolgivesaresultwhich isacombinationoffreewaterandextractedwaterofcrystallizationfromthefollowingcomponentsoffertilizers: calciumnitratetetrahydrate(Ca(NO 3 ) 2 4H 2 O);calciumhydrogenphosphatedihydrate(CaHPO 4 2
20、H 2 O);calcium sulfatedihydrate(gypsum,CaSO 4 2H 2 O)calciumsulfatehemihydrate(CaSO 4 0,5H 2 O);magnesiumsulfate heptahydrate(MgSO 4 7H 2 O);potassiumchloridemagnesiumsulfatewater(1/1/2,75,Kainite, KClMgSO 4 2,75H 2 O);potassiummagnesiumsulfatehexahydrate(Schoenite,K 2 SO 4 MgSO 4 6H 2 O);potassium
21、magnesiumsulfatetetrahydrate(Leonite,K 2 SO 4 MgSO 4 4H 2 O);potassiumsulfatecalciumsulfatemonohydrate (Syngenite,K 2 SO 4 CaSO 4 H 2 O);potassiumchloridemagnesiumchloridehexahydrate(Carnallite,KCl MgCl 2 6H 2 O);magnesiumnitratehexahydrate(Mg(NO 3 ) 2 6H 2 O). Extractionwith2propanolgivesaresultwhi
22、chisacombinationoffreewaterandextractedwaterofcrystallization fromthefollowingcomponentsoffertilizers:calciumnitratetetrahydrate(Ca(NO 3 ) 2 4H 2 O);magnesiumsulfate heptahydrate(MgSO 4 7H 2 O);potassiumchloridemagnesiumchloridehexahydrate(Carnallite,KClMgCl 2 6H 2 O); magnesiumnitratehexahydrate(Mg
23、(NO 3 ) 2 6H 2 O).EN134661:2001(E) 5 1Scope ThisEuropeanStandardspecifiesaKarlFischertitrimetricmethodforthedeterminationofthewatercontentof fertilizersbasedontheuseofmethanolasextractingmedium. Themethodisapplicabletoallsolidmineralfertilizers.Theresult(KFMwater)includes“free“waterand extracted wat
24、erofcrystallizationfromthefollowingcomponentsoffertilizers:calciumnitratetetrahydrate(Ca(NO 3 ) 2 4H 2 O); calciumhydrogenphosphatedihydrate(CaHPO 4 2H 2 O);calciumsulfatedihydrate(gypsum,CaSO 4 2H 2 O),calcium sulfatehemihydrate(CaSO 4 0,5H 2 O);magnesiumsulfateheptahydrate(MgSO 4 7H 2 O);potassium
25、chloride magnesiumsulfatewater(1/1/2,75,Kainite,KClMgSO 4 2,75H 2 O);potassiummagnesiumsulfatehexahydrate (Schoenite,K 2 SO 4 MgSO 4 6H 2 O);potassiummagnesiumsulfatetetrahydrate(Leonite,K 2 SO 4 MgSO 4 4H 2 O); potassiumsulfatecalciumsulfatemonohydrate(Syngenite,K 2 SO 4 CaSO 4 H 2 O);potassiumchlo
26、ridemagnesium chloridehexahydrate(Carnallite,KClMgCl 2 6H 2 O);magnesiumnitratehexahydrate(Mg(NO 3 ) 2 6H 2 O). Metaloxidesandhydroxidessolubleinmethanolandpyridinewillhaveaneffectwhichcanbecorrectedfor,iftheir contentisknown. 2 Normativereferences ThisEuropeanStandardincorporatesbydatedorundatedref
27、erence,provisionsfromotherpublications.These normativereferencesarecitedattheappropriateplacesinthetext,andthepublicationsarelistedhereafter.For datedreferences,subsequentamendmentstoorrevisionsofanyofthesepublicationsapplytothisEuropean Standardonlywhenincorporatedinitbyamendmentorrevision.Forundat
28、edreferencesthelatesteditionofthe publicationreferredtoapplies(includingamendments). EN1482, Samplingofsolidfertilizersandlimingmaterials. 3Principle ExtractionofwaterfromthefertilizerintomethanolandtitrationofthewaterwithaKarlFischerreagent,previously standardizedbytitrationwithaknownmassofwater. 4
29、Reagents 4.1General Allreagentsshallbeofrecognizedanalyticalgrade. 4.2 Methanol,containingnomorethanamassconcentrationof500mg/lwater. 4.3 KarlFischerreagent ,equivalencefrom1mgto5mgwater/mlreagent(seeTables1and2). 4.4 Sodiumtartratedihydrate Na 2 C 4 H 4 O 6 2H 2 O(15,66%massfractionofwater). Sodium
30、tartratedihydrateNa 2 C 4 H 4 O 6 2H 2 Ocanbestoredover60%H 2 SO 4 inadesiccator.Checkthewater contentbydryingatabout150C. 5Apparatus Ordinarylaboratoryapparatusandglasswareandinparticularthefollowing: 5.1 Balance,capableofweighingtothenearest0,0001g.EN134661:2001(E) 6 5.2 Mortarand pestle. 5.3 Cent
31、rifugecapableofoperatingatarateof3500min 1 . 5.4 Centrifugetubes ,diameter4,5cm,height10cmfittedwithrubberstoppers. 5.5Dispersing apparatus :turbinetype,minimumrotationalfrequency9500min 1 ,suitableforintroductioninto centrifugetubes(5.4),forinstanceUltraTurrax 1 5.6 KarlFischertitrator NOTE Therear
32、eseveraltitratorsonthemarketfortheKarlFischermethod. 6 InstallationandtestoftheKarlFischertitrator Followtheinstructionmanualfortheparticulartitratorused. 7Sampling CarryoutsamplinginaccordancewithEN1482. 8Procedure 8.1CalibrationoftheKarlFischerreagent Titrateaknownamountofwaterorsodiumtartratedihy
33、drate(4.4)accuratelyweighedtothenearest0,0001g followingtheinstructionmanualforthetitrator. NOTE Calibrationfrequencyshouldbeadaptedtothefrequencyofanalysis. 8.2Drift ControlthediffusionofwaterfromtheairintothetitrationvesselduringthedeterminationfollowingtheInstruction Manualforthetitrator.Takeacco
34、untofanyrecordeddrift( m d )whenexpressingresults. 8.3Determination 8.3.1General Ifthefertilizerisdispersibleinmethanol(4.2),theextractionandtitrationcanbecarriedoutinthetitrationvessel (see8.3.2).Ifnot,aseparateextractionstepwillbeneeded(see8.3.3). Urea,ammoniumnitrateandCAN(=calciumammoniumnitrate
35、)areusuallydispersibleinmethanol. 8.3.2 Fertilizersdispersibleorsolubleinmethanol 8.3.2.1 Preparationoftestportion Rapidlycrushthetestsamplepreparedinaccordancewithclause7andimmediatelyweighatestportion(see Table1)tothenearest0,0001g. 1 UltraTurraxS25 equippedwithdispersingturbineS25KR18Gisanexample
36、ofequipmentcommercially available.ThisinformationisgivenfortheconvenienceofusersofthisEuropeanStandardanddoesnotconstitute anendorsementbyCENoftheseproducts.EN134661:2001(E) 7 NOTE Productssuchasureaandammoniumnitratewhicharefullysolubleinmethanolshouldnotbecrushed. Table1Massoftestportionforfertili
37、zersdispersibleorsolubleinmethanol Massoftestportion Expectedwatercontent massfractionin% titreofKFReagent 5mg/ml titreofKFReagent 2mg/ml 20to50 0,2g 8.3.2.2Titration Introduce20mlofmethanol(4.2)intothereactionvesselofthetitrator(5.6). Introducetheweighedtestportion(8.3.2.1)directlyintothereactionve
38、sselofthetitrator(5.6).Startstirringand ensure,thatthegrainsofthefertilizerarefullydispersed.TitratewiththeKarlFischerreagent(4.3)untilthe equivalencepointisreachedfollowingtheinstructionmanualforthetitrator.Recordthemass m s ,inmilligramsof water,indicatedbythetitrator.Adaptthedeadtimeofthetitrator
39、tothegrainsizeofthedispersedfertilizerin accordancewiththeinstructionmanualofthetitratorused. 8.3.3 Fertilizersnotdispersibleinmethanol 8.3.3.1 Testportion Weighatestportionofthetestsample,inaccordancewithclause7andTable2tothenearest0,0001gdirectly intothepreviouslydriedandtaredcentrifugetube(5.4).
40、Table2Massoftestportionforfertilizersnotdispersibleinmethanol Massoftestportion Expectedwatercontent massfractionin% titreofKFReagent 5mg/ml titreofKFReagent 2mg/ml 20to50 1g 8.3.3.2Extraction Add25mlofmethanol(4.2)withacalibratedpipettetothetestportioninthecentrifugetube.Insertthedispersing apparat
41、us(5.5)ensuringthatthedistancefromanypartofthedispersingtooltotheinnersurfaceofthecentrifuge tubeisgreaterthanthegrainsizeofthefertilizer. Placethedispersingtoolneartothesurfaceofthefertilizerlayer.Dispersefor60satroomtemperatureat 9500min 1 atleast. Makesurethatthetemperatureduringthedispersionextr
42、actiondoesnotexceed40Cor,incaseoffertilizer containingmagnesiumsulfate,25C. Repeatthedispersionforafurther60sifthefertilizerhasnotbeencompletelydispersedinthefirstoperation. Repeattheextractionifthedispersionisstillnotcomplete. NOTE Thedispersioncanbecontrolledacoustically;theturbinepitchchangesonce
43、thedispersioniscomplete.EN134661:2001(E) 8 8.3.3.3Separation Removethedispersionapparatusfromthecentrifugetubeandstopperthelatterwiththerubberstopper. Centrifugethetubefor5min.Repeatfor5minifthesupernatantliquidisnotclear. 8.3.3.4 Titration Introduce5,0mloftheclearsolution(8.3.3.3)intothereactionvesselofthetitrator(5.6).Startstirring.Titratewith theKarlFischerreagent(4.3)untiltheequivalencepointisreachedfollowingtheinstructionmanualforthetitrator. Recordthemass m s , inmilligramsofwater,indicatedbythetitrator. 8.4Blanktest Carryoutablanktestfollowingtheprocedurespec
