1、November 2010 Translation by DIN-Sprachendienst.English price group 11No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).I
2、CS 65.080!$l1X“1731453www.din.deDDIN EN 15909Fertilizers Determination of calcium and formate in calcium foliar fertilizersEnglish translation of DIN EN 15909:2010-11Dngemittel Bestimmung von Calcium und Formiat in Calcium-BlattdngemittelnEnglische bersetzung von DIN EN 15909:2010-11Engrais Dosage d
3、u calcium et du formiate dans les engrais calcium pour pulvrisation foliaireTraduction anglaise de DIN EN 15909:2010-11www.beuth.deDocument comprises pagesIn case of doubt, the German-language original shall be considered authoritative.1710.10 DIN EN 15909:2010-11 2 A comma is used as the decimal ma
4、rker. National foreword This standard has been prepared by Technical Committee CEN/TC 260 “Fertilizers and liming materials” (Secretariat: DIN, Germany) under the mandate M/418. The responsible German body involved in its preparation was the Normenausschuss Lebensmittel und landwirtschaftliche Produ
5、kte (Food and Agricultural Products Standards Committee), Working Committee NA 057-03-02 AA Dngemittel. The DIN Standards corresponding to the International Standards referred to in this document are as follows, whereby EN ISO Standards are only listed below if these have not been published as DIN E
6、N ISO Standards with the same number: EN ISO 3696 DIN ISO 3696 ISO 5725-1 DIN ISO 5725-1 ISO 5725-2 DIN ISO 5725-2 National Annex NA (informative) Bibliography DIN ISO 3696, Water for analytical laboratory use Specification and test methods DIN ISO 5725-1, Accuracy (trueness and precision) of measur
7、ement methods and results Part 1: General principles and definitions DIN ISO 5725-2, Accuracy (trueness and precision) of measurement methods and results Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method EUROPEAN STANDARD NORME EUROPENNE
8、 EUROPISCHE NORM EN 15909 June 2010 ICS 65.080 English Version Fertilizers - Determination of calcium and formate in calcium foliar fertilizers Engrais - Dosage du calcium et du formiate dans les engrais calcium pour pulvrisation foliaire Dngemittel - Bestimmung von Calcium und Formiat in Calcium-Bl
9、attdngemitteln This European Standard was approved by CEN on 29 April 2010. 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 lists and biblio
10、graphical references concerning such national standards 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 translation under the responsibility o
11、f a CEN member into its own language and notified to the CEN 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, France, Germany, Greece, Hungary, Icel
12、and, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue
13、 Marnix 17, B-1000 Brussels 2010 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 15909:2010: EEN 15909:2010 (E) 2 Contents Page Foreword 31 Scope 42 Normative references 43 Terms and definitions .44 Principle 44.1 General 44.2 Calc
14、ium .44.3 Formate .54.4 Chloride 55 Reagents .56 Apparatus .67 Sampling and sample preparation .68 Procedure .78.1 Preparation of the test solution 78.2 Determination of the calcium content (concentration C1) 78.3 Determination of formate content (concentration C2) .88.3.1 HPLC conditions 88.3.2 Elu
15、tion conditions88.3.3 Detection conditions .88.3.4 Procedure .98.3.5 Calculation 98.4 Determination of chloride content (concentration C3) 98.4.1 Instrument settings for the automatic titroprocessor (6.3) .98.4.2 Stop conditions . 108.4.3 Evaluation 108.4.4 Preparation of sodium chloride solution 0,
16、01 mol/l (for blank value determination) 108.4.5 Preparation of methyl orange indicator solution 108.4.6 Procedure 108.4.7 Calculation . 118.4.8 Adjustment of correction factor (titre) of 0,01 mol/l silver nitrate solution with sodium chloride (5.12) 119 Calculation and expression of the result . 12
17、9.1 Stoichiometric data. 129.2 Expression of the result . 129.3 Determination of residual content of calcium (9.2.3) 1210 Precision 1310.1 Inter-laboratory test 1310.2 Repeatability 1310.3 Reproducibility 1311 Test report . 13Annex A (informative) Statistical results of the inter-laboratory tests .
18、14Bibliography . 15DIN EN 15909:2010-11 EN 15909:2010 (E) 3 Foreword This document (EN 15909:2010) 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,
19、 either by publication of an identical text or by endorsement, at the latest by December 2010, and conflicting national standards shall be withdrawn at the latest by December 2010. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. C
20、EN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association According to the CEN/CENELEC Internal Regulations, the national standards org
21、anizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, P
22、ortugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. DIN EN 15909:2010-11 EN 15909:2010 (E) 4 1 Scope This European Standard specifies a method for the determination of the content of calcium and formate in calcium foliar fertilizers in the presence of calcium chl
23、oride. This is determined and calculated by individual analytical determination of the following components: Calcium (Ca2+), Chloride (Cl-), Formate (HCOO-). The method is applicable to calcium foliar fertilizers with a calcium content of approximately 30 %. 2 Normative references The following refe
24、renced 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 480-10, Admixtures for concrete, mortar and grout Test methods P
25、art 10: Determination of water soluble chloride content 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 Vocabulary Part 1: General terms EN 12944-2:1999, Fertilizers and liming
26、 materials and soil improvers Vocabulary Part 2: Terms relating to fertilizers EN ISO 3696:1995, Water for analytical laboratory use Specification and test methods (ISO 3696:1987) 3 Terms and definitions For the purposes of this document, the terms and definitions given in EN 12944-1:1999 and EN 129
27、44-2:1999 apply. 4 Principle 4.1 General Three different analytical procedures are used for the determination of the components to be determined, calcium, formate and chloride, in calcium foliar fertilizers. The substances calcium formate and calcium chloride are calculated stoichiometrically from t
28、he analytical results determined in each case (4.2, 4.3 and 4.4) (see Clause 9). 4.2 Calcium The calcium content is determined complexometrically with the diluted sample in strongly alkaline solution by means of adjusted 0,1 mol/l EDTA solution (5.1) and the calcium-specific indicator, calconcarboxy
29、lic acid (8.2). DIN EN 15909:2010-11 EN 15909:2010 (E) 5 4.3 Formate The formate content is determined isocratically by reversed phase HPLC on the basis of the diluted sample (see 8.3). Evaluation is carried out with external standard. 4.4 Chloride The chloride content is determined by potentiometri
30、c titration according to the following reaction (see 8.4); the sample is first diluted, acetone is added and then the sample is acidified with acetic acid: Cl-+ Ag+ AgCl (solid) After each addition of AgNO3the measured potentials are measured and recorded using a titroprocessor. The endpoint is reac
31、hed when the differential quotient E/V, i. e. the potential change E observed for each volume step V, reaches its greatest value. This point can be determined using a titroprocessor or voltmeter. In this titration the chloride ions which are determined include other water-soluble halogen ions apart
32、from fluorides. The total halogen content is designated chloride content. See EN 480-10 for the principles. 5 Reagents Use only reagents of recognized analytical grade and distilled or demineralized water (grade 3 according to EN ISO 3696:1995). 5.1 EDTA solution, (ethylenedinitrilotetraacetic acid
33、disodiumsalt dehydrate), c(EDTA) = 0,1mol/l. 5.2 Calcium carbonate, reference material for complexometry. 5.3 Calconcarboxylic acid, indicator for metal titration. 5.4 Methyl orange. 5.5 Sodium chloride, p. a. 5.6 Sodium hydroxide solution, p. a., = 45 %. 5.7 Water, purified. 5.8 Ortho-phosphoric ac
34、id, p. a., w = 85 %. 5.9 Formate standard solution, for ion chromatography, = 1 000 mg/l1). 5.10 Silver nitrate solution, c(AgNO3) = 0,01 mol/l. 5.11 Diluted hydrochloric acid, p.a., dilute 1 volume of hydrochloric acid, w = 37 %, with 1 volume of water (5.7). 5.12 Sodium chloride, certified primary
35、 reference material. 5.13 Diluted acetic acid, dilute 1 volume of acetic acid, w = 98 % to 100 %, with 1 volume of water (5.7). 5.14 Acetone, p.a. 1) Fluka Art. No: 49897-100 ML-F is an example of a suitable product available commercially. This information is given for the convenience of users of th
36、is document and does not constitute an endorsement by CEN of this product. DIN EN 15909:2010-11 EN 15909:2010 (E) 6 5.15 Magnesium sulfate, anhydrous p.a. 6 Apparatus 6.1 Analytical balance, accuracy of 1 mg. 6.2 HPLC apparatus, equipped with an automatic sample injection system, UV detector and eva
37、luation system. 6.3 Titroprocessor2). 6.3.1 Dosimat, 10 ml exchange unit, for 0,01 mol/l sodium chloride solution (8.4.4). 6.3.2 Dosimat, 20 ml exchange unit, for 0,01 mol/l silver nitrate solution (5.11). 6.3.3 Silver ring electrode3). 6.4 Volumetric flask, capacity 100 ml. 6.5 Volumetric flask, ca
38、pacity 1 000 ml. 6.6 Bulb pipette, capacity 10 ml. 6.7 Bulb pipette, capacity 20 ml. 6.8 Bulb pipette, capacity 25 ml. 6.9 Bulb pipette, capacity 100 ml. 6.10 Burette, capacity 25 ml. 6.11 Agate mortar. 6.12 Magnetic stirrer. 6.13 Glass beaker, capacity 50 ml. 6.14 Glass beaker, capacity 250 ml. 6.1
39、5 Glass beaker, capacity 600 ml. 6.16 Weighing dishes. 7 Sampling and sample preparation Sampling is not part of the method specified in this document. A recommended sampling method is given in EN 1482-1. Sample preparation shall be carried out in accordance with EN 1482-2. 2) Metrohm DMS-Titrino 71
40、6 is an example of a suitable product available commercially. This information is given for the convenience of users of this document and does not constitute an endorsement by CEN of this product. 3) Metrohm 6.0430.100 is an example of a suitable product available commercially. This information is g
41、iven for the convenience of users of this document and does not constitute an endorsement by CEN of this product. DIN EN 15909:2010-11 EN 15909:2010 (E) 7 8 Procedure 8.1 Preparation of the test solution Transfer approximately 1 000 mg 10 mg of the sample to be determined, accurately weighed to 0,1
42、mg, to a weighing dish (6.16) (weight m). Transfer the test portion from the weighing dish to the volumetric flask (6.5) by rinsing with distilled water. Make the volumetric flask up to the mark with distilled water at 20C, and dissolve (solution R1). 8.2 Determination of the calcium content (concen
43、tration C1) 8.2.1 Using a bulb pipette (6.9), transfer 100 ml of solution R1 (8.1) to a glass beaker (6.15), and make up to 400 ml with distilled water. 8.2.2 Render the solution alkaline (pH 12) with 10 ml of sodium hydroxide solution (5.6). 8.2.3 Add approximately 0,3 g of indicator (8.2.6) to the
44、 alkaline solution and, immediately after dissolution, titrate with adjusted EDTA solution (5.1) until the colour changes from red to green (6.10 and 6.12). Consumption: ml 0,1 mol/l EDTA solution (V1). The colour change can be improved significantly by adding a spatula tipful (approximately 20 mg t
45、o 40 mg) of magnesium sulfate (5.15). 8.2.4 Blank value: proceed as described in 8.2.2 and 8.2.3 with 400 ml of distilled water. Consumption: ml 0,1 mol/l EDTA solution (V2). 8.2.5 Calculation Calculate the calcium content, wCa, in percent (mass fraction) according to the following equation: mtVVw=0
46、00 110010008 4,)(Ca21(1) where V1is the consumption of 0,1 mol/l EDTA solution for sample, in millilitre; V2is the consumption of 0,1 mol/l EDTA solution for blank value, in millilitre; 4,008 is 1/10 g/mol calcium; t is the correction factor for 0,1 mol/l EDTA solution; 10 is the aliquot portion; 10
47、0 is the factor for conversion to percent; 1 000 is the 0,1 mol/l EDTA solution (stoichiometric to 1/10 g/mol calcium) in millilitre; m is the mass of the test portion in grams (8.1). 8.2.6 Preparation of the indicator Triturate 0,10 g of calconcarboxylic acid (5.3), 0,05 g of methyl orange (5.4) an
48、d 9,85 g of sodium chloride (5.5) in the agate mortar (6.11) to a homogenous powder. 8.2.7 Adjustment of correction factor (titre), for 0,1 mol/l EDTA solution (5.1) DIN EN 15909:2010-11 EN 15909:2010 (E) 8 Transfer 0,19 g to 0,21 g of calcium carbonate (5.2), accurately weighed to 0,1 mg, to a glas
49、s beaker (6.15), and dissolve in 50 ml of distilled water, if necessary adding a few drops of hydrochloric acid (5.11) until the solution is clear. Dry the calcium carbonate (5.2) at 120C for at least 2 h before use. Subsequently, make up to 400 ml with distilled water, and proceed as described in 8.2.2 to 8.2.4. Calculate the correction factor, t, according to the
