EN 13368-2-2017 en Fertilizers - Determination of chelating agents in fertilizers by chromatography - Part 2 Determination of Fe chelated by [o o] EDDHA [o o] EDDHMA and HBED or th.pdf

1、BSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06Fertilizers - Determination of chelating agents in fertilizers by chromatographyPart 2: Determination of Fe chelated by o,o EDDHA, o,o EDDHMA and HBED, or the amount of chelating agents, by ion pair chromatographyBS EN

2、13368-2:2017EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 13368-2 November 2017 ICS 65.080 Supersedes EN 13368-2:2012English Version Fertilizers - Determination of chelating agents in fertilizers by chromatography - Part 2: Determination of Fe chelated by o,o EDDHA, o,o EDDHMA and HBED, or th

3、e amount of chelating agents, by ion pair chromatography Engrais - Dtermination des agents chlatants dans les engrais par chromatographie - Partie 2 : Dtermination du fer chlat o,o EDDHA, o,o EDDHMA et HBED, ou de la quantit dagents chlatants, par chromatographie dappariement dions Dngemittel - Best

4、immung von Chelatbildnern in Dngemitteln mit Chromatographie - Teil 2: Bestimmung von Fe chelatisiertem o,o EDDHA, o,o EDDHMA und HBED, oder der Summe der Chelatbildner, mit Ionen-Paarchromatographie This European Standard was approved by CEN on 11 September 2017. CEN members are bound to comply wit

5、h the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Manag

6、ement 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 translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same sta

7、tus as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malt

8、a, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels

9、2017 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 13368-2:2017 ENational forewordThis British Standard is the UK implementation of EN 133682:2017. It supersedes BS EN 133682:2012, which is withdrawn.The UK participation in its p

10、reparation was entrusted to Technical Committee CII/37, Fertilisers and related chemicals.A list of organizations represented on this committee can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsible f

11、or its correct application. The British Standards Institution 2017 Published by BSI Standards Limited 2017ISBN 978 0 580 94078 1ICS 65.080Compliance with a British Standard cannot confer immunity from legal obligations.This British Standard was published under the authority of the Standards Policy a

12、nd Strategy Committee on 30 November 2017.Amendments/corrigenda issued since publicationDate Text affectedBRITISH STANDARDBS EN 133682:2017EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 13368-2 November 2017 ICS 65.080 Supersedes EN 13368-2:2012English Version Fertilizers - Determination of ch

13、elating agents in fertilizers by chromatography - Part 2: Determination of Fe chelated by o,o EDDHA, o,o EDDHMA and HBED, or the amount of chelating agents, by ion pair chromatography Engrais - Dtermination des agents chlatants dans les engrais par chromatographie - Partie 2 : Dtermination du fer ch

14、lat o,o EDDHA, o,o EDDHMA et HBED, ou de la quantit dagents chlatants, par chromatographie dappariement dions Dngemittel - Bestimmung von Chelatbildnern in Dngemitteln mit Chromatographie - Teil 2: Bestimmung von Fe chelatisiertem o,o EDDHA, o,o EDDHMA und HBED, oder der Summe der Chelatbildner, mit

15、 Ionen-Paarchromatographie This European Standard was approved by CEN on 11 September 2017. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date

16、lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC 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 translation un

17、der the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former

18、 Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION

19、COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2017 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 13368-2:2017 EBS EN 133682:2017EN 13368-2:2017 (E)

20、2 Contents Page European foreword . 4 1 Scope 6 2 Normative references 6 3 Terms and definitions . 6 4 Principle . 7 5 Interferences 7 6 Reagents . 7 7 Apparatus . 9 8 Sampling and sample preparation 9 9 Procedure 10 9.1 Preparation of the sample solution for iron chelates . 10 9.2 Preparation of th

21、e sample solution for other micronutrient chelates . 10 9.3 Preparation of the calibration solutions . 10 9.4 Chromatographic analysis 11 10 Expression of the results . 14 10.1 Fe in Fe-chelates . 14 10.1.1 Fe chelated by o,o EDDHA or o,o EDDHMA in Fe-o,o EDDHA or Fe-o,o EDDHMA chelates 14 10.1.2 Fe

22、 chelated by HBED in Fe-HBED chelates 15 10.2 Chelating agent in fertilizers 15 10.2.1 Mass fraction of the chelating agent in fertilizers containing o,o EDDHA or o,o EDDHMA 15 10.2.2 Mass fraction of the chelating agent in fertilizers containing HBED . 16 11 Precision 16 11.1 Inter-laboratory test

23、. 16 11.2 Repeatability 16 11.3 Reproducibility . 16 12 Test report 18 Annex A (informative) Statistical results of the inter-laboratory tests . 19 A.1 Statistical results of the inter-laboratory test performed in 2003 19 A.1.1 Test samples 19 A.1.2 Inter-laboratory test procedure . 19 A.1.3 Results

24、 and statistical interpretation . 19 A.2 Statistical results of the inter-laboratory test performed in 2010 21 A.2.1 Test samples 21 A.2.2 Inter-laboratory test procedure . 21 A.2.3 Results and statistical interpretation . 21 BS EN 133682:2017EN 13368-2:2017 (E) 3 A.3 Statistical results of the inte

25、r-laboratory test performed in 2014 Part A 22 A.3.1 Objective 22 A.3.2 Test samples . 22 A.3.3 Inter-laboratory test procedure 22 A.3.4 Results and statistical interpretation . 22 A.4 Statistical results of the inter-laboratory test performed in 2014 Part B 24 A.4.1 Objective 24 A.4.2 Test samples .

26、 24 A.4.3 Inter-laboratory test procedure 25 A.4.4 Results and statistical interpretation . 25 Annex B (informative) General procedure for the determination of the titrimetric purity of the chelating agents using a photometric automatic titrator . 26 Annex C (informative) Complete names of chelating

27、 agents . 27 Bibliography . 28 BS EN 133682:2017EN 13368-2:2017 (E) 4 European foreword This document (EN 13368-2:2017) 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

28、 a national standard, either by publication of an identical text or by endorsement, at the latest by May 2018 and conflicting national standards shall be withdrawn at the latest by May 2018. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent

29、 rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. This document supersedes EN 13368-2:2012. This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association. In comparison with EN 13

30、368-2:2012, the following changes have been made: a) determination of the chelating agent added to the scope and to the title; b) a derivatization method for the determination of the chelating agent explained in Clause 4, Principle; c) a new option added for the preparation of the Fe-o,o EDDHA solut

31、ion, starting from a Fe-o,o EDDHA standard, in 6.6; d) calculation of the mass fraction of the chelating agents included in Clause 10 including Formulae (3) and (4); e) Table 2 enlarged by the precision data concerning the 2014 inter-laboratory test; f) information on the type of standard used for F

32、e-o,o EDDHA samples and the possibility to report on the chelating agent contents included in Clause 12; g) results of the inter-laboratory test performed in 2014, part A and B respectively, added (A.3 and A.4); h) complete names of chelating agents in Annex C technically revised; i) editorially rev

33、ised. EN 13368, Fertilizers Determination of chelating agents in fertilizers by chromatography consists of the following parts: Part 1: Determination of EDTA, HEEDTA and DTPA by ion chromatography Part 2: Determination of Fe chelated by o,o EDDHA, o,o EDDHMA and HBED, or the amount of chelating agen

34、ts, by ion pair chromatography Part 3: Determination of S,S-EDDS by ion pair chromatography BS EN 133682:2017EN 13368-2:2017 (E) 5 According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria

35、, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain,

36、Sweden, Switzerland, Turkey and the United Kingdom. BS EN 133682:2017EN 13368-2:2017 (E) 6 1 Scope This European Standard 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, o,o EDDHM

37、A and by HBED in fertilizers containing one or more of these substances, except for o,o EDDHMA and HBED mixes. The method allows the identification and the determination of the total concentration of water soluble iron chelates of these chelating agents. Also, after derivatization with Fe, the solub

38、le amount of the chelating agents can be determined when other micro-nutrients, beside Fe are present in fertilizers containing o,o EDDHA, o,o EDDHMA or HBED. This method is applicable to EC fertilizers covered by Regulation (EC) No 2003/2003 4. It is applicable to a mass fraction of the metal chela

39、ted of at least 0,625 %. NOTE 1 The substances EDDHA (ethylenediamine-N,N-di(hydroxyphenyl)acetic acid and EDDHMA (ethylenediamine-N,N-di(hydroxymethylphenyl)acetic acid exist as several different isomeric forms. Positional isomers for the hydroxyl or methyl groups (in ortho, meta, and para position

40、s) 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 E

41、DDHMA 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. HBED (N,N-bis(2-hydroxybenzyl)-ethylenediamine-N,N-diacetic acid) does not present isomeric forms. NOTE 2 At presen

42、t, analytically pure standards only exist for ortho,ortho EDDHA, ortho,ortho EDDHMA and HBED. 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

43、3 The meso and the dl-racemic forms of o,o EDDHA and o,o EDDHMA can be determined separately by this method. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edit

44、ion 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 12944-1:1999, Fertilizers and liming materials and soil improvers

45、 - Vocabulary - Part 1: General terms EN 12944-2:1999, Fertilizers and liming materials and soil improvers - Vocabulary - Part 2: Terms relating to fertilizers EN ISO 3696, Water for analytical laboratory use - Specification and test methods (ISO 3696) 3 Terms and definitions For the purposes of thi

46、s document, the terms and definitions given in EN 12944-1:1999 and EN 12944-2:1999 apply. BS EN 133682:2017EN 13368-2:2017 (E) 7 4 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 f

47、luid (eluent), containing a large cation, an ion pair is formed. This ion pair is retained by a non-polar 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 che

48、lating 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. For metal chelates differe

49、nt from Fe, a derivatization method may be used to form the Fe chelates, and then the chelating agent can be determined by the isocratic ion-pair high-performance liquid chromatography here presented. NOTE For additional information, see 5, 6 and 7. 5 Interferences No interferences have been detected. Iron chelates with HBEP, EDDHSA, EDTA, DTPA, CDTA, HEEDTA, p,p EDDHA, o,p EDDHA, IDHA as well as the chelating agents do not interfere