1、July 2010 Translation by DIN-Sprachendienst.English price group 9No 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).ICS 65
2、.080!$iJ?“1703928www.din.deDDIN EN 14397-1Fertilizers and liming materials Determination of carbon dioxide Part 1: Method for solid fertilizersEnglish translation of DIN EN 14397-1:2010-07Dngemittel und Calcium-/Magnesium-Bodenverbesserungsmittel Bestimmung von Kohlenstoffdioxid Teil 1: Verfahren fr
3、 feste DngemittelEnglische bersetzung von DIN EN 14397-1:2010-07Engrais et amendements minraux basiques Dtermination de la teneur en dioxyde de carbone Partie 1: Mthode applicable aux engrais solidesTraduction anglaise de DIN EN 14397-1:2010-07SupersedesDIN CEN/TS 14397-1:2004-11www.beuth.deIn case
4、of doubt, the German-language original shall be considered authoritative.Document comprises 13 pages07.10 DIN EN 14397-1:2010-07 2 A comma is used as the decimal marker. National foreword This standard has been prepared by Technical Committee CEN/TC 260 “Fertilizers and liming materials” (Secretaria
5、t: DIN, Germany) under the mandate M/335. The responsible German body involved in its preparation was the Normenausschuss Lebensmittel und landwirtschaftliche Produkte (Food and Agricultural Products Standards Committee), Working Committee NA 057-03-02 AA Dngemittel. The DIN Standards corresponding
6、to the European and International Standards referred to in this document are as follows: EN ISO 3696 DIN ISO 3696 ISO 5725-2 DIN ISO 5725-2 Amendments This standard differs from DIN CEN/TS 14397-1:2004-11 as follows: a) Based on the results of the unique acceptance procedure, the document has been a
7、dopted as a European Standard. b) Normative references have been updated. the inter-laboratory tests” has been added. Previous editions DIN CEN/TS 14397-1: 2004-11 National Annex NA (informative) Bibliography DIN ISO 3696, Water for analytical laboratory use Specification and test methods DIN ISO 57
8、25-2, 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 c) Clause 9 “Precision” has been added. d) Annex A (informative) “Results ofe) A bibliography has been added. EU
9、ROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 14397-1 March 2010 ICS 65.080 Supersedes CEN/TS 14397-1:2004English Version Fertilizers and liming materials - Determination of carbon dioxide - Part 1: Method for solid fertilizers Engrais et amendements minraux basiques - Dtermination de la teneur
10、 en dioxyde de carbone - Partie 1: Mthode applicable aux engrais solides Dngemittel und Calcium-/Magnesium-Bodenverbesserungsmittel - Bestimmung von Kohlenstoffdioxid - Teil 1: Verfahren fr feste DngemittelThis European Standard was approved by CEN on 14 February 2010. CEN members are bound to compl
11、y 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 bibliographical references concerning such national standards may be obtained on application to the CEN Manageme
12、nt 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 Management Centre has the same status as the
13、official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania,
14、 Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2010 CEN All rights of exploitation in any form and by any means reserved worl
15、dwide for CEN national Members. Ref. No. EN 14397-1:2010: EEN 14397-1:2010 (E) 2 Contents Page Foreword 31 Scope 42 Normative references 43 Principle 44 Reagents .45 Apparatus .56 Sampling and sample preparation .67 Procedure .67.1 Test portion 77.2 Determination .77.3 Blank test 78 Expression of re
16、sults 79 Precision .89.1 Inter-laboratory test .89.2 Repeatability .89.3 Reproducibility .810 Test report 9Annex A (informative) Results of the inter-laboratory tests 10Bibliography . 11DIN EN 14397-1:2010-07 EN 14397-1:2010 (E) 3 Foreword This document (EN 14397-1:2010) has been prepared by Technic
17、al 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 September 2010, and conflicting national standa
18、rds shall be withdrawn at the latest by September 2010. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. This document supersedes CEN/T
19、S 14397-1:2004. This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association. The following text has been added to the former edition of the European Standard: a) Clause 9 “Precision“; b) Annex A “Results of the inter-laboratory test
20、s“. 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, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ire
21、land, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. DIN EN 14397-1:2010-07 EN 14397-1:2010 (E) 4 1 Scope This document specifies a method for the determination of carbon dioxide in s
22、olid fertilizers. The method applies to all fertilizers that contain carbonates and/or bicarbonates. NOTE If the fertilizer contains any other substances that release carbon dioxide on treatment with phosphoric acid, this will also be determined and expressed as carbon dioxide. 2 Normative reference
23、s 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 Sam
24、pling and sample preparation Part 2: Sample preparation EN ISO 3696:1995, Water for analytical laboratory use Specification and test methods (ISO 3696:1987) 3 Principle The carbon dioxide is liberated by treatment with phosphoric acid and absorbed in a solution of barium hydroxide. Barium carbonate
25、precipitates and the excess barium hydroxide is back-titrated with hydrochloric acid. 4 Reagents Use only reagents of recognized analytical grade. 4.1 Water, conforming to EN ISO 3696:1995, grade 3. Boil the water immediately before use, to drive off any dissolved carbon dioxide. 4.2 Nitrogen, with
26、a low content of carbon dioxide and organic impurities. 4.3 Hydrochloric acid, standard volumetric solution, c(HCl) = 0,1 mol/l. 4.4 Barium hydroxide, standard volumetric solution, c(Ba(OH)2) = 0,05 mol/l approximately. Standardize the barium hydroxide solution by titrating against the hydrochloric
27、acid solution (4.3), using the phenolphthalein solution (4.6) as indicator. NOTE The barium hydroxide solution should be stored so that absorption of carbon dioxide from the atmosphere is not possible (see Figure 1). 4.5 Phosphoric acid, with a volume concentration of = 500 ml/l. 4.6 Phenolphthalein
28、 solution. DIN EN 14397-1:2010-07 EN 14397-1:2010 (E) 5 5 Apparatus Usual laboratory apparatus and the following are required. 5.1 Analytical balance, capable of weighing to an accuracy of 0,1 mg. 5.2 Laboratory grinder or mortar and pestle. 5.3 Burette, for barium hydroxide solution (see Figure 1).
29、 Key 1 reservoir and burette 2 washing flask, 250 ml, filled with soda lime pellets and indicator Figure 1 Burette for barium hydroxide solution 5.4 Glassware assembly, as shown in Figure 2, comprising the following: a) flow meter for nitrogen (1); b) pressure relief tube with 850 mm water column (2
30、); c) washing flasks with 250 ml capacity, filled with soda lime pellets and indicator (3); d) 500 ml reservoir for phosphoric acid with rubber ball used as acid dosing unit (4); e) round-bottom, three-necked reaction flask fitted with a splash head (5); f) three absorption vessels, each of 250 ml c
31、apacity, with fritted glass tubes to ensure full absorption of the liberated carbon dioxide (7), (8), (9). The frit in the first vessel (7) should be coarse enough to avoid blockage during the absorption. Alternatively, the frit may be replaced by a mushroom bubbler with small holes. DIN EN 14397-1:
32、2010-07 EN 14397-1:2010 (E) 6 Key 1 flow meter for nitrogen 2 pressure relief tube 3 washing flasks 4 500 ml reservoir for phosphoric acid with rubber ball 5 three-necked reaction flask fitted with a splash head 6 hot plate (with magnetic stirrer and oil bath) 7,8,9 absorption vessels with fritted g
33、lass tubes Figure 2 Apparatus for carbon dioxide absorption 5.5 Weighing boat. 5.6 Hot plate, see (6) in Figure 2. 6 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
34、 out in accordance with EN 1482-2. Prepare the sample to obtain a laboratory sample of at least 100 g. Grind the laboratory sample to give a test sample with a particle size of less than 200 m and mix thoroughly. 7 Procedure SAFETY PRECAUTIONS Appropriate precautions should be taken to avoid harmful
35、 compounds, which can be given off during the phosphoric acid treatment, from getting into the laboratory atmosphere. DIN EN 14397-1:2010-07 EN 14397-1:2010 (E) 7 7.1 Test portion Weigh in the weighing boat (5.5), to the nearest 0,1 mg, an amount of the test sample containing not more than 40 mg of
36、carbon dioxide. As a guide, the test portion should be no more than 200 mg for calcium ammonium nitrate (CAN) and 90 mg for dolomite. 7.2 Determination Carefully assemble the apparatus shown in Figure 2 ensuring there are no leaks. Purge the entire apparatus with nitrogen (4.2) for 30 min. Disconnec
37、t the three absorption vessels in the order (9), (8) and (7) whilst maintaining the nitrogen stream. Pipette into each vessel 50 ml of the barium hydroxide solution (4.4). Reconnect the vessels to the apparatus and purge for a further 5 min. Disconnect the bulb and flexible tube and add 20 ml of pho
38、sphoric acid solution (4.5) to the acid-dosing unit (4). Introduce the test portion (7.1) to the round bottom three-necked reaction flask (5) through the stopper. Rinse the weighing boat and the neck of the stopper into the flask using 20 ml to 25 ml of water. Reduce the nitrogen flow to five litre
39、per hour. Create an overpressure in the reservoir with the rubber ball so that by opening the valve of the acid-dosing unit (4) the phosphoric acid passes to the round bottom reaction flask (5). Start the magnetic stirrer and heat the contents of the round bottom reaction flask (5) by means of the h
40、ot plate (5.6) to boiling and boil gently for 2 h. Ensure that the temperature in the flask does not exceed 100 C. Discontinue heating and disconnect the absorption vessels in the order (9), (8) and (7). Rinse the absorption vessels from above with water. Slowly back-titrate the excess barium hydrox
41、ide in each absorption vessel with the hydrochloric acid (4.3) using the phenolphthalein solution (4.6) as indicator. Carry out the titration under nitrogen, to prevent absorption of carbon dioxide from the atmosphere. NOTE Local excesses of hydrochloric acid should be avoided as these can dissolve
42、some of the precipitated barium carbonate. Magnetic stirring during the titration helps to minimize the local excess of acid. If the equivalent of more than 1 ml of barium hydroxide solution in absorption vessel (9) has been consumed by reaction with carbon dioxide, repeat the determination with a r
43、educed flow of nitrogen. 7.3 Blank test Carry out a blank test by the procedure described in 7.2 but omitting the test portion (7.1). 8 Expression of results Calculate the mass fraction of carbon dioxide, wCO2, expressed in grams of carbon dioxide per kilogram of fertilizer, using the following equa
44、tion: mcVcVcVcVw000 144222b,21b,12211CO2= (1) where V1 is the volume, in millilitres, of barium hydroxide solution added to the three absorption vessels (150 ml); DIN EN 14397-1:2010-07 EN 14397-1:2010 (E) 8 V2 is the total volume, in millilitres, of hydrochloric acid used in the back-titration; c1i
45、s the amount-of-substance concentration, in moles per litre, of the barium hydroxide solution; c2is the amount-of-substance concentration, in moles per litre, of the hydrochloric acid solution; V1,b is the volume, in millilitres, barium hydroxide added to the three absorption vessels during the blan
46、k test; V2,bis the total volume, in millilitres, of hydrochloric acid solution used in the back-titration during the blank test; m is the mass, in milligrams, of the test portion. 9 Precision 9.1 Inter-laboratory test An inter-laboratory test was carried out in 2002 with 8 participating laboratories
47、 and five different samples of fertilizers and phosphate types. This test yielded the data given in Annex A. Repeatability and reproducibility were calculated according to ISO 5725-2. The values derived from this inter-laboratory test might not be applicable to concentration ranges and matrices othe
48、r than those given in Annex A. 9.2 Repeatability The absolute difference between two independent single test results, obtained with the same method on identical test material in the same laboratory by the same operator using the same equipment within a short interval of time, will exceed, in not mor
49、e than 5 % of the cases, the values of r given in Table 1. 9.3 Reproducibility The absolute difference between two single test results, obtained with the same method on identical test material in different laboratories by different operators using different equipment, will exceed, in not more than 5 % of the cases, the values of R given in Table 1. Table 1 Mean values, repeatability and reproducibility limits Sample x % r % R % CA
