SIST EN 13368-2:2007
Fertilizers - Determination of chelating agents in fertilizers by chromatography - Part 2: Determination of Fe chelated by o,o-EDDHA and o,o-EDDHMA by ion pair chromatography
Fertilizers - Determination of chelating agents in fertilizers by chromatography - Part 2: Determination of Fe chelated by o,o-EDDHA and o,o-EDDHMA by ion pair chromatography
This document specifies a method for the chromatographic determination of the iron chelated by each individual ortho(hydroxy)-ortho(hydroxy) isomer of the chelating agents o,o-EDDHA and o,o-EDDHMA in fertilizers containing one or both of these substances. The method allows the identification and the determination of the total concentration of water soluble iron chelates of these chelating agents. It does not determine the free form of the chelating agents.
NOTE 1 The substances EDDHA (ethylene diamine di(hydroxy phenyl) acetic acid) and EDDHMA (ethylene diamine di(hydroxy methyl phenyl)acetic acid) exist as several different isomeric forms. Positional isomers for the hydroxyl or methyl groups (in ortho, meta, and para positions) as well as stereo isomers (meso and dl-racemic forms) are known. Both meso and dl-racemic forms of the ortho,ortho-EDDHA and ortho,ortho-EDDHMA are positional isomers for the hydroxyl groups allowed by the Regulation (EC) No 2003/2003. Since para, meta and ortho methyl positional isomers of the EDDHMA present quite similar stability, they could be grouped: in the method here described the para, meta and ortho methyl positional isomers of the o,o-EDDHMA are considered together.
NOTE 2 At present, analytically pure standards only exist for ortho,ortho-EDDHA and ortho,ortho-EDDHMA. All other substances being unavailable as a standard, the influence of their eventual presence in the samples (with respect to the sensitivity and the selectivity of this method) has not been studied.
NOTE 3 The meso and the dl-racemic forms of o,o-EDDHA and o,o-EDDHMA can be determined separately by this method.
This procedure concerns EC fertilizers covered by Regulation (EC) No 2003/2003 [5]. It is applicable to a mass fraction of the metal chelated of at least 0,625 %.
Düngemittel - Bestimmung von Chelatbildnern in Düngemitteln mit Chromatographie - Teil 2: Bestimmung von Fe chelatisiertem o,o-EDDHA und o,o-EDDHMA mit lonen-Paarchromatographie
Dieses Dokument legt ein Verfahren zur chromatographischen Bestimmung des Ions, das mit den einzelnen
Ortho(hydroxy)-ortho(hydroxy)-Isomeren der Chelatbildner o,o-EDDHA und o,o-EDDHMA Chelate bildet, in
Düngemitteln fest, die eine dieser oder beide Substanzen enthalten. Das Verfahren ermöglicht die Identifi-
zierung und die Bestimmung der Gesamtkonzentration von wasserlöslichen Eisenchelaten dieser Chelat-
bildner. Es erlaubt nicht die Bestimmung der freien Form der Chelatbildner.
ANMERKUNG 1 Die Substanzen EDDHA (Ethylendiamin-di-(hydroxyphenyl)essigsäure) und EDDHMA (Ethylendiamin-
di-(hydroxymethylphenyl)essigsäure) existieren in mehreren unterschiedlichen isomeren Formen. Es sind sowohl
Stellungsisomere (in Ortho-, Meta- und Parastellungen) als auch Stereoisomere (Meso- und dl-Racemformen) der
Hydroxyl- und Methylgruppen bekannt. Die Meso- und dl-Racemformen von Ortho-ortho-EDDHA und Ortho-ortho-
EDDHMA sind Stellungsisomere der Hydroxylgruppen, die nach der Verordnung (EG) Nr. 2003/2003 zugelassen sind. Da
Para-, Meta- und Orthomethyl-Stellungsisomere von EDDHMA eine ziemlich ähnliche Stabilität aufweisen, könnten sie in
einer Gruppe zusammengefasst werden: in dem hier beschriebenen Verfahren werden Para-, Meta- und Orthomethyl-
Stellungsisomere von o,o-EDDHMA zusammen betrachtet.
ANMERKUNG 2 Gegenwärtig existieren analysenreine Standards nur für Ortho-ortho-EDDHA und Ortho-ortho-
EDDMHA. Da alle anderen Substanzen als Standards nicht zur Verfügung stehen, ist der Einfluss von deren eventueller
Anwesenheit in den Proben (in Bezug auf die Empfindlichkeit und die Trennschärfe dieses Verfahrens) noch nicht
untersucht worden.
ANMERKUNG 3 Mit diesem Verfahren können die Meso- und dl-Racemformen von o,o-EDDHA und o,o-EDDHMA
einzeln bestimmt werden.
Engrais - Détermination des agents chélatants dans les engrais par chromatographie - Partie 2 : Détermination du fer chélaté par o,o-EDDHA et o,o-EDDHMA par chromatographie avec appariement d'ions
Le présent document spécifie une méthode de détermination par chromatographie du fer chélaté par chacun des isomeres ortho(hydroxy)-ortho(hydroxy) des agents chélatants o,o-EDDHA et o,o-EDDHMA dans les engrais contenant l’une de ces substances ou les deux. La méthode permet l’identification et la détermination de la concentration totale de ces agents en chélates de fer solubles dans l’eau. Elle ne permet pas de déterminer ces agents chélatants sous leur forme libre.
NOTE 1 Les substances EDDHA (acide éthylenediamine-di(hydroxyphényl)acétique) et EDDHMA (acide éthylenediamine di(hydroxy-méthylphényl)acétique) existent sous plusieurs formes isomeres différentes. On connaît les isomeres de position des groupes hydroxyl et méthyl (en position ortho, méta et para) et les stéréo-isomeres (formes méso et dl-racémiques). Les deux formes méso et dl-racémiques de l’ortho-ortho-EDDHA et de l’ortho-ortho-EDDHMA sont des isomeres de position des groupes hydroxyl autorisés par la réglementation (CE) n° 2003/2003. Dans la mesure ou les isomeres de position ortho, méta et para des groupes méthyl de l’EDDHMA présentent une stabilité tout a fait similaire, ils ont pu etre regroupés. Dans la méthode décrite ici, les isomeres de position ortho, méta et para des groupes méthyl de l’o,o-EDDHMA sont donc considérés conjointement.
NOTE 2 A l’heure actuelle, il n’existe de produit de référence pur pour analyse que pour l’ortho-ortho-EDDHA et l’ortho ortho-EDDHMA. Aucune autre substance n’étant pas disponible en tant que produit de référence, l’influence de leur présence éventuelle dans les échantillons n’a fait l’objet d’aucune étude (du point de vue de la sensibilité et de la sélectivité de la méthode).
NOTE 3 Les formes méso et dl-racémiques de o,o-EDDHA et o,o-EDDHMA peuvent etre déterminées séparément par la présente méthode.
Le mode opératoire décrit concerne les engrais européens couverts par la Réglementation CE n°2003/2003 [5]. Il est applicable a une teneur en métal chélaté d’a
Gnojila - Določevanje sredstev za kelatiziranje v gnojilih s kromatografijo - 2. del: Določevanje železovih kelatov z o,o-EDDHA in o,o-EDDHMA z ionsko kromatografijo
General Information
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Standards Content (Sample)
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Fertilizers - Determination of chelating agents in fertilizers by chromatography - Part 2: Determination of Fe chelated by o,o-EDDHA and o,o-EDDHMA by ion pair chromatographyNURPDWRJUDILMREngrais - Détermination des agents chélatants dans les engrais par chromatographie - Partie 2 : Détermination du fer chélaté par o,o-EDDHA et o,o-EDDHMA par chromatographie avec appariement d'ionsDüngemittel - Bestimmung von Chelatbildnern in Düngemitteln mit Chromatographie - Teil 2: Bestimmung von Fe chelatisiertem o,o-EDDHA und o,o-EDDHMA mit lonen-PaarchromatographieTa slovenski standard je istoveten z:EN 13368-2:2007SIST EN 13368-2:2007en,fr,de65.080GnojilaFertilizersICS:SIST EN 13368-2:20021DGRPHãþDSLOVENSKI
STANDARDSIST EN 13368-2:200701-september-2007
EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 13368-2April 2007ICS 65.080Supersedes EN 13368-2:2001
English VersionFertilizers - Determination of chelating agents in fertilizers bychromatography - Part 2: Determination of Fe chelated by o,o-EDDHA and o,o-EDDHMA by ion pair chromatographyEngrais - Détermination des agents chélatants dans lesengrais par chromatographie - Partie 2: Détermination dufer chélaté o,o-EDDHA ou o,o-EDDHMA parchromatographie avec appariement d'ionsDüngemittel - Bestimmung von Chelatbildnern inDüngemitteln mit Chromatographie - Teil 2: Bestimmungvon Fe chelatisiertem o,o-EDDHA und o,o-EDDHMA mitlonen-PaarchromatographieThis European Standard was approved by CEN on 24 February 2007.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the CEN Management Centre or to any CEN member.This European Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own language and notified to the CEN Management Centre has the same status as theofficial versions.CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre: rue de Stassart, 36
B-1050 Brussels© 2007 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 13368-2:2007: E
EN 13368-2:2007 (E) 2 Contents Page Foreword.3 1 Scope.4 2 Normative references.4 3 Principle.4 4 Interferences.5 5 Reagents.5 6 Apparatus.6 7 Preparation of the sample.7 8 Procedure.7 9 Expression of the results (Fe in Fe-chelates).11 10 Precision.11 11 Test report.13 Annex A (informative)
General procedure for the determination of the titrimetric purity of the chelating agents using a photometric automatic titrator.14 Annex B (informative)
Results of the inter-laboratory test.15 Annex C (informative)
Complete names of chelating agents.17 Bibliography.18
EN 13368-2:2007 (E) 3 Foreword This document (EN 13368-2:2007) has been prepared by Technical Committee CEN/TC 260 “Fertilizers and liming materials”, the secretariat of which is held by DIN. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by October 2007, and conflicting national standards shall be withdrawn at the latest by October 2007. This document supersedes EN 13368-2:2001. EN 13368:2001 consisted of two parts: Fertilizers — Determination of chelating agents in fertilizers by ion chromatography — Part 1: EDTA, HEDTA and DTPA Fertilizers — Determination of chelating agents in fertilizers by ion chromatography — Part 2: EDDHA and EDDHMA For technical reasons, the second element in the title of this document has been modified (the word “ion” has been deleted). Consequently, the title of Part 1 of EN 13368 should be revised in the same way. There is agreement that the replacement of Part 1 by a new edition only for harmonization of the title should be avoided. Therefore, it is proposed to harmonize the title within the next revision procedure. Following the revised title of Part 2, the title of EN 13368-1 should be revised as follows: Fertilizers — Determination of chelating agents in fertilizers by chromatography — Part 1: Determination of EDTA, HEDTA and DTPA According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
EN 13368-2:2007 (E) 4 1 Scope This document specifies a method for the chromatographic determination of the iron chelated by each individual ortho(hydroxy)-ortho(hydroxy) isomer of the chelating agents o,o-EDDHA and o,o-EDDHMA in fertilizers containing one or both of these substances. The method allows the identification and the determination of the total concentration of water soluble iron chelates of these chelating agents. It does not determine the free form of the chelating agents. NOTE 1 The substances EDDHA (ethylene diamine di(hydroxy phenyl) acetic acid) and EDDHMA (ethylene diamine di(hydroxy methyl phenyl)acetic acid) exist as several different isomeric forms. Positional isomers for the hydroxyl or methyl groups (in ortho, meta, and para positions) as well as stereo isomers (meso and dl-racemic forms) are known. Both meso and dl-racemic forms of the ortho,ortho-EDDHA and ortho,ortho-EDDHMA are positional isomers for the hydroxyl groups allowed by the Regulation (EC) No 2003/2003. Since para, meta and ortho methyl positional isomers of the EDDHMA present quite similar stability, they could be grouped: in the method here described the para, meta and ortho methyl positional isomers of the o,o-EDDHMA are considered together. NOTE 2 At present, analytically pure standards only exist for ortho,ortho-EDDHA and ortho,ortho-EDDHMA. All other substances being unavailable as a standard, the influence of their eventual presence in the samples (with respect to the sensitivity and the selectivity of this method) has not been studied. NOTE 3 The meso and the dl-racemic forms of o,o-EDDHA and o,o-EDDHMA can be determined separately by this method. This procedure concerns EC fertilizers covered by Regulation (EC) No 2003/2003 [5]. It is applicable to a mass fraction of the metal chelated of at least 0,625 %. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN 1482-2, Fertilizers and liming materials — Sampling and sample preparation — Part 2: Sample preparation EN ISO 3696, Water for analytical laboratory use — Specification and test methods (ISO 3696:1987) 3 Principle The iron chelates are separated and determined by isocratic ion-pair high-performance liquid chromatography. When an iron chelate (anion) is added to a polar fluid (eluent), containing a large cation, an ion pair is formed. This ion pair is retained by an apolar solid phase (stationary phase). The strength of the retention depends on the molecular size and its acidity. Then, each iron chelate presents a characteristic retention time depending on the chelating agent, and it is separated from the other substances present in the sample. The separation is carried out on a reverse phase silica column and an aqueous solution of TBA+ (tetrabutylammonium) and acetonitrile as eluent. The detection is based on photometry at 280 nm. NOTE For additional information see [3] and [4].
EN 13368-2:2007 (E) 5
4 Interferences No interferences have been detected. Iron chelates with HBED, HBEP, EDDHSA, EDTA, DTPA, CDTA, HEDTA, p,p-EDDHA, o,p-EDDHA, as well as the chelating agents do not interfere since they are separated from Fe-o,o-EDDHA and Fe-o,o-EDDHMA. NOTE For the complete names of the abbreviations of chelating agents used in this document see Annex C. 5 Reagents 5.1 General a) All reagents shall be of recognized analytical grade; b) all water used for the preparation of eluent, standards, and sample solutions shall conform to EN ISO 3696, grade 1 and shall be degassed, and free of organic contaminants; c) if for the preparation of standard solutions products with a declared purity of less than 99 % are used, a correction should be made in order to obtain exactly the required concentration in the solution. If there is any doubt of the purity of the standard, it is necessary to determine it. NOTE For this determination a titrimetric method can be used. See Annex A for a general method using an automatic titrator. Manual titration could be also adequate. 5.2 Sodium hydroxide solution, c(NaOH) = 0,1 mol/l. Dissolve 4 g of NaOH in pellet form in a 1 litre volumetric flask with water (see 5.1 b)). Dilute to the mark and homogenize. NOTE The incorporation of CO2 from the atmosphere should be carefully avoided. Otherwise dissolution of chelating agents (see 5.5) can be incomplete. 5.3 Hydrochloric acid solution, c(HCl) = 1,0 mol/l. Dilute 88 ml of hydrochloric acid (mass fraction 35 % HCl) to 1 000 ml with water. 5.4 Hydrochloric acid solution, c(HCl) = 0,1 mol/l. Dilute 50 ml of hydrochloric acid 1,0 mol/l (5.3) to 500 ml with water.
EN 13368-2:2007 (E) 6
5.5 Fe-o,o-EDDHA solution, ρ(Fe) = 100 mg/l. Dissolve 0,759 4 g of ferric nitrate 9-hydrate (Fe(NO3)3·9H2O) in 100 ml of water. Check (for example by AAS) that the Fe concentration in this solution is 1 050 mg ± 30 mg Fe/l. NOTE As the Fe(NO3)3·9H2O is deliquescent it will be added in solution of a known concentration. Dissolve 0,322 1 g (see 5.1.) of ethylene diamine di(o-hydroxy phenyl)acetic acid in 350 ml of water and 27 ml of NaOH (5.2) in a 500 ml beaker. Add 50 ml of the Fe solution to the chelating agent solution stirring for about 5 min. Adjust the solution to pH 7,0 with NaOH solution (5.2). Let the solution stand overnight in darkness to allow excess Fe to precipitate as oxide. Filter quantitatively through a cellulose filter and make up to volume (500 ml) in a volumetric flask with water. The standard obtained in this way can be stored in darkness for one year. 5.6 Fe-o,o-EDDHMA solution, ρ(Fe) = 100 mg/l. Dissolve 0,347 1 g (see 5.1) of ethylene diamine di(o-hydroxy-p-methyl phenyl)acetic acid (o,o-EDDHMA) in 350 ml of water and 27 ml of NaOH (5.2) in a 500 ml beaker. Add 50 ml of the Fe solution to the chelating agent solution stirring for about 5 min. Adjust the solution to pH 7,0 with NaOH solution (5.2). Let the solution stand overnight in darkness to allow excess Fe to precipitate as oxide. Filter quantitatively through a cellulose filter and make up to volume (500 ml) in a volumetric flask with water. The standard obtained in this way can be stored in darkness for one year. 5.7 Eluent for the determi
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