1、BS EN14397-1:2010ICS 65.080NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBRITISH STANDARDFertilizers andliming materials Determination ofcarbon dioxidePart 1: Method for solid fertilizersThis British Standardwas published under theauthority of the StandardsPolicy and Strategy
2、Committee on 30 June2010 BSI 2010ISBN 978 0 580 68162 2Amendments/corrigenda issued since publicationDate CommentsBS EN 14397-1:2010National forewordThis British Standard is the UK implementation of EN 14397-1:2010.The UK participation in its preparation was entrusted to TechnicalCommittee CII/37, F
3、ertilisers and related chemicals.A list of organizations represented on this committee can be obtained onrequest to its secretary.This publication does not purport to include all the necessary provisionsof a contract. Users are responsible for its correct application.Compliance with a British Standa
4、rd cannot confer immunityfrom legal obligations.BS EN 14397-1:2010EUROPEAN 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
5、 Engrais et amendements minraux basiques - Dtermination de la teneur 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
6、 approved by CEN on 14 February 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 bibliographical references concerning such n
7、ational 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 of a CEN member into its own language a
8、nd 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, Iceland, Ireland, Italy, Latvia, Lithuania
9、, 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 Marnix 17, B-1000 Brussels 2010 CEN A
10、ll rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 14397-1:2010: EBS EN 14397-1:2010EN 14397-1:2010 (E) 2 Contents Page Foreword 31 Scope 42 Normative references 43 Principle 44 Reagents .45 Apparatus .56 Sampling and sample preparation .6
11、7 Procedure .67.1 Test portion 77.2 Determination .77.3 Blank test 78 Expression of results 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 . 11BS EN 14397-1:2010EN 14397-1
12、:2010 (E) 3 Foreword This document (EN 14397-1:2010) 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, either by publication of an identical text or
13、 by endorsement, at the latest by September 2010, and conflicting national standards 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 responsi
14、ble for identifying any or all such patent rights. This document supersedes CEN/TS 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 St
15、andard: a) Clause 9 “Precision“; b) Annex A “Results of the inter-laboratory tests“. 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 Re
16、public, 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 the United Kingdom. BS EN 14397-1:2010EN 14397-1:2010 (E) 4 1 Scope T
17、his document specifies a method for the determination of carbon dioxide in solid 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 wi
18、ll also be determined and expressed as carbon dioxide. 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 (includ
19、ing any amendments) applies. EN 1482-2, Fertilizers and liming materials Sampling 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 phosp
20、horic acid and absorbed in a solution of barium hydroxide. Barium carbonate 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 immediatel
21、y before use, to drive off any dissolved carbon dioxide. 4.2 Nitrogen, with 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. Stan
22、dardize the barium hydroxide solution by titrating against the hydrochloric 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 Pho
23、sphoric acid, with a volume concentration of = 500 ml/l. 4.6 Phenolphthalein solution. BS EN 14397-1:2010EN 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
24、 and pestle. 5.3 Burette, for barium hydroxide solution (see Figure 1). 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 mete
25、r for nitrogen (1); b) pressure relief tube with 850 mm water column (2); 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 fitte
26、d with a splash head (5); f) three absorption vessels, each of 250 ml capacity, 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
27、may be replaced by a mushroom bubbler with small holes. BS EN 14397-1:2010EN 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 magn
28、etic stirrer and oil bath) 7,8,9 absorption vessels with fritted glass 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
29、 method is given in EN 1482-1. Sample preparation shall be carried 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 PR
30、ECAUTIONS Appropriate precautions should be taken to avoid harmful compounds, which can be given off during the phosphoric acid treatment, from getting into the laboratory atmosphere. BS EN 14397-1:2010EN 14397-1:2010 (E) 7 7.1 Test portion Weigh in the weighing boat (5.5), to the nearest 0,1 mg, an
31、 amount of the test sample containing not more than 40 mg of 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 t
32、he entire apparatus with nitrogen (4.2) for 30 min. Disconnect 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 mi
33、n. Disconnect the bulb and flexible tube and add 20 ml of phosphoric 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
34、ml to 25 ml of water. Reduce the nitrogen flow to five litre 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 cont
35、ents of the round bottom reaction flask (5) by means of the hot 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 a
36、bove with water. Slowly back-titrate the excess barium hydroxide 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
37、of hydrochloric acid should be avoided as these can dissolve 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 re
38、action with carbon dioxide, repeat the determination with a reduced 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
39、 dioxide per kilogram of fertilizer, using the following equation: mcVcVcVcVw000 144222b,21b,12211CO2= (1) where V1 is the volume, in millilitres, of barium hydroxide solution added to the three absorption vessels (150 ml); BS EN 14397-1:2010EN 14397-1:2010 (E) 8 V2 is the total volume, in millilitr
40、es, of hydrochloric acid used in the back-titration; c1is 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 hydroxi
41、de added to the three absorption vessels during the blank 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 w
42、as carried out in 2002 with 8 participating laboratories 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
43、 be applicable to concentration ranges and matrices other 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
44、within a short interval of time, will exceed, in not more 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 us
45、ing 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 % CAN 8,0 0,8 1,4Dolomite 40,4 1,7 9,3 Nitromag 15,6 0,8 2,3NK 10,4 0,9 1,8 NPK 4,01 0,44 0,61BS EN 14397-1:2010EN
46、 14397-1:2010 (E) 9 10 Test report The test report shall contain at least the following information: a) all information necessary for the complete identification of the sample; b) test method used with reference to this European Standard; c) test results obtained expressed in grams of carbon dioxide
47、 per kilogram of fertilizer; d) date of sampling and sampling procedure (if known); e) date when the analysis was finished; f) whether the requirement of the repeatability limit has been fulfilled; g) all operating details not specified in this European Standard, or regarded as optional, together wi
48、th details of any incidents occurred when performing the method which might have influenced the test result(s). BS EN 14397-1:2010EN 14397-1:2010 (E) 10 Annex A (informative) Results of the inter-laboratory tests The precision of the method was established in 2002 by Task Force 1 “Carbon dioxide” of
49、 CEN/TC 260 “Fertilizers and liming materials” in an inter-laboratory test evaluated in accordance with ISO 5725-2. The statistical results are given in Table A.1. Table A.1 Statistical results of the inter-laboratory test Parameter Sample CAN Dolomite Nitromag NK NPK Number of participating laboratories 8 8 8 8 8 Number of laboratories after elimination of outliers (accepted test results) 7 6 6 6 6 Mean value x (%) 8,0 40,4 15,6 10,4 4,01 Repeata
