1、Fertilizers Determination of molybdenum in concentrations 10 % using a gravimetric method with 8- hydroxyquinolinePD CEN/TS 17060:2017BSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE SPEZIFIKATION CEN/TS 17060
2、May 2017 ICS 65.080 English Version Fertilizers - Determination of molybdenum in concentrations 10 % using a gravimetric method with 8-hydroxyquinoline Engrais - Dosage du molybdne dans des concentrations 10 % en utilisant une mthode gravimtrique la 8-hydroxyquinoline Dngemittel - Bestimmung von Mol
3、ybdn in Konzentrationen 10 % durch Gravimetrie mit 8-Hydroxychinolin This Technical Specification (CEN/TS) was approved by CEN on 3 March 2017 for provisional application. The period of validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be requested
4、to submit their comments, particularly on the question whether the CEN/TS can be converted into a European Standard. CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS available promptly at national level in an appropriate form. It i
5、s permissible to keep conflicting national standards in force (in parallel to the CEN/TS) until the final decision about the possible conversion of the CEN/TS into an EN is reached. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark,
6、 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, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMI
7、TTEE FOR STANDARDIZATION 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. CEN/TS 17060:2017 ENational f
8、orewordThis Published Document is the UK implementation of CEN/TS 17060:2017.The UK participation in its preparation 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 p
9、ublication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2017 Published by BSI Standards Limited 2017ISBN 978 0 580 92806 2ICS 65.080Compliance with a British Standard cannot confer immunit
10、y from legal obligations. This Published Document was published under the authority of the Standards Policy and Strategy Committee on 31 August 2017.Amendments/corrigenda issued since publicationDate Text affectedPUBLISHED DOCUMENTPD CEN/TS 17060:2017TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TE
11、CHNISCHE SPEZIFIKATION CEN/TS 17060 May 2017 ICS 65.080 English Version Fertilizers - Determination of molybdenum in concentrations 10 % using a gravimetric method with 8-hydroxyquinoline Engrais - Dosage du molybdne dans des concentrations 10 % en utilisant une mthode gravimtrique la 8-hydroxyquino
12、line Dngemittel - Bestimmung von Molybdn in Konzentrationen 10 % durch Gravimetrie mit 8-Hydroxychinolin This Technical Specification (CEN/TS) was approved by CEN on 3 March 2017 for provisional application. The period of validity of this CEN/TS is limited initially to three years. After two years t
13、he members of CEN will be requested to submit their comments, particularly on the question whether the CEN/TS can be converted into a European Standard. CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS available promptly at nationa
14、l level in an appropriate form. It is permissible to keep conflicting national standards in force (in parallel to the CEN/TS) until the final decision about the possible conversion of the CEN/TS into an EN is reached. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croat
15、ia, 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, Sweden, Switzerland, Turke
16、y 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 2017 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Re
17、f. No. CEN/TS 17060:2017 EPD CEN/TS 17060:2017CEN/TS 17060:2017 (E) 2 Contents Page European foreword . 3 Introduction 4 1 Scope 5 2 Normative references 5 3 Terms and definitions . 5 4 Principle . 5 5 Sampling and sample preparation 5 6 Reagents . 6 7 Apparatus . 6 8 Procedure. 7 8.1 Preparation of
18、 the test solution . 7 8.2 Precipitation . 7 8.3 Filtration and washing 7 8.4 Weighing the precipitate 7 9 Calculation and expression of the results 7 10 Test report . 8 Annex A (informative) Verification gravimetric method to ICP-AES method 9 Bibliography . 12 PD CEN/TS 17060:2017CEN/TS 17060:2017
19、(E) 3 European foreword This document (CEN/TS 17060:2017) has been prepared by Technical Committee CEN/TC 260 “Fertilizers and liming materials”, the secretariat of which is held by DIN. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rig
20、hts. CEN 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 organisatio
21、ns of the following countries are bound to announce this Technical Specification: 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, M
22、alta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. PD CEN/TS 17060:2017CEN/TS 17060:2017 (E) 4 Introduction The preparation of this document by CEN is based on a mandate by the European Commission and the Europ
23、ean Free Trade Association (Mandate M/335), concerning the modernization of methods of analysis on fertilizers in the framework of Regulation (EC) No 2003/2003 1. This document is part of a modular approach and concerns the analytical measurement step. “Modular” means that a test standard concerns a
24、 specific step in assessing a property and not the whole chain of measurements. Determination of molybdenum in fertilizers can be executed by inductively coupled plasma-atomic emission spectrometry (ICP-AES) according to prEN 16963:2016. The gravimetric determination as molybdenyl oxinate is more la
25、bour intensive and skill demanding but it is an option when ICP-AES is not available. WARNING Persons using this European Technical Specification should be familiar with normal laboratory practice. This European Technical Specification does not purport to address all of the safety issues, if any, as
26、sociated with its use. It is the responsibility of the user to establish appropriate health and safety practices and to ensure compliance with any national regulatory conditions. IMPORTANT It is absolutely essential that tests conducted according to this European Technical Specification are carried
27、out by suitably trained staff. PD CEN/TS 17060:2017CEN/TS 17060:2017 (E) 5 1 Scope This Technical Specification specifies a method for the determination of total and water extractable molybdenum in mineral fertilizers containing more than 10 % molybdenum. This method is applicable to water and aqua
28、regia fertilizer extracts obtained according to prEN 16962:2016 and/or prEN 16964:2016. 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 edition cited applies. Fo
29、r 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, Fertilizers and liming materials and soil improvers - Vocabulary - Part 1: Ge
30、neral terms EN 12944-2, Fertilizers and liming materials and soil improvers - Vocabulary - Part 2: Terms relating to fertilizers prEN 16962:2016, Fertilizers Extraction of water soluble micro-nutrients in fertilizers and removal of organic compounds from fertilizer extracts prEN 16964:2016, Fertiliz
31、ers Extraction of total micro-nutrients in fertilizers and removal of organic compounds from fertilizer extracts EN ISO 3696, Water for analytical laboratory use - Specification and test methods (ISO 3696) ISO 4793, Laboratory sintered (fritted) filters Porosity grading, classification and designati
32、on 3 Terms and definitions For the purposes of this document, the terms and definitions given in EN 12944-1 and EN 12944-2 apply. 4 Principle The molybdenum content is determined by precipitation as molybdenyl oxinate under specific conditions. 5 Sampling and sample preparation Sampling is not part
33、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. The sample extracts shall be prepared in accordance with prEN 16962:2016 and/or prEN 16964:2016. PD CEN/TS 17060:2017CEN/TS 17060:2017
34、(E) 6 6 Reagents All reagents shall be of recognized analytical grade and shall have negligible concentrations of molybdenum if compared to the lowest concentration of that element in the sample solution. 6.1 Water, according to EN ISO 3696 grade 2. 6.2 Sulfuric acid, H2SO4, = 1,84 g/ml. 6.3 Sulfuri
35、c acid solution, approximately 1 mol/l. Carefully pour 55 ml of sulfuric acid (6.2) into a 1 l volumetric flask (7.5) containing 800 ml water (6.1). Mix. After cooling, make up to 1 l. Mix again. 6.4 Concentrated ammonia solution, NH4OH, = 0,9 g/ml. 6.5 Diluted ammonia solution, volume fraction rati
36、o = 1:3. Mix 1 volume of concentrated ammonia solution (6.4) with 3 volumes of water (6.1). 6.6 Concentrated acetic acid, 99,7 % CH3COOH, = 1,049 g/ml. 6.7 Diluted acetic acid solution, volume fraction ratio = 1:3. Mix 1 volume of concentrated acetic acid (6.6) with 3 volumes of water (6.1). 6.8 Sol
37、ution of disodium salt of ethylenediamine tetraacetic acid (Na2EDTA). Dissolve 5 g of Na2EDTA in water (6.1) in a 100 ml volumetric flask (7.4). Make up to the calibration mark and mix. 6.9 Buffer solution. In a 100 ml volumetric flask (7.4), dissolve 15 ml of concentrated acetic acid (6.6) and 30 g
38、 of ammonium acetate in water (6.1). Make up to 100 ml. 6.10 8-Hydroxyquinoline (oxine) solution. In a 100 ml volumetric flask (7.4), dissolve 3 g of 8-Hydroxyquinoline in 5 ml of concentrated acetic acid (6.6). Add 80 ml of water (6.1). Add the diluted ammonia solution (6.5) drop by drop until the
39、solution becomes cloudy and then add the diluted acetic acid (6.7) until the solution becomes clear again. Make up to 100 ml with water (6.1). 7 Apparatus 7.1 Filter crucible, P16 according to ISO 4793, porosity 4, capacity 30 ml. 7.2 pH meter with glass electrode. 7.3 Drying oven, set at (130 to 13
40、5) C. 7.4 Volumetric flasks, capacity 100 ml. 7.5 Volumetric flasks, capacity 1 l. 7.6 Beaker, capacity 250 ml. 7.7 Desiccator. PD CEN/TS 17060:2017CEN/TS 17060:2017 (E) 7 8 Procedure 8.1 Preparation of the test solution Place an aliquot portion containing 10 mg Mo to 100 mg Mo, maximum 50 ml, in a
41、250 ml beaker (7.6). Make up the volume to 50 ml with water (6.1). Adjust this solution to pH 5, measured by the pH meter (7.2) by adding the sulfuric acid solution (6.3) or diluted ammonia solution (6.5) drop by drop. Add 15 ml of EDTA solution (6.8) followed by 5 ml of buffer solution (6.9). Make
42、up to about 80 ml with water (6.1). 8.2 Precipitation Heat the solution (8.1) slightly. Stirring constantly, add slowly the oxine solution (6.10) and continue the precipitation until formation of a deposit is no longer observed. Add further reagent until the supernatant solution turns slightly yello
43、w. A quantity of 20 ml of oxine solution (6.10) should normally be sufficient. Continue to heat the precipitate slightly for 2 min or 3 min. 8.3 Filtration and washing Dry the filter crucible (7.1) at (130 to 135) C to constant mass (at least 1 h) and weigh the crucible (m1). Filter the solution wit
44、h the precipitate (8.2) through a filter crucible (7.1). Rinse the precipitate several times with 20 ml of hot water (6.1). The rinse water should gradually become colourless indicating that oxine is no longer present. 8.4 Weighing the precipitate Dry the precipitate at (130 to 135) C to constant ma
45、ss (at least 1 h). Allow to cool in a desiccator (7.7) and then weigh (m2). 9 Calculation and expression of the results 1 mg of molybdenyl oxinate, MoO2(C9H6ON)2, corresponds to 0,230 5 mg Mo. The content of molybdenum, wMo, in the fertilizer is calculated as a mass fraction in percent according to
46、Formula (1). ( )Mo0,02305X VDwaM =(1) where X is the mass in mg of the molybdenyl oxinate precipitate X = m2 m1; V is the volume in ml of the extract solution; a is the volume in ml of the aliquot taken from the last dilution; D is the dilution factor of the aliquot; M is the mass in g of the test s
47、ample. PD CEN/TS 17060:2017CEN/TS 17060:2017 (E) 8 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) the test method used with reference to this document, CEN/TS 17060; c) the method of prep
48、aration of the extraction solution; d) the test results obtained; e) date of sampling and sampling procedure (if known); f) date when the analysis was finished; g) whether the requirement of the repeatability limit has been fulfilled; h) all operating details not specified in this document, or regar
49、ded as optional, together with details of any incidents occurred when performing the method, which might have influenced the test result(s). PD CEN/TS 17060:2017CEN/TS 17060:2017 (E) 9 Annex A (informative) Verification gravimetric method to ICP-AES method A.1 Introduction and test materials used The gravimetric determination of molybdenum in concentrations 10 % is more labour intensive than the determination using ICP-AES according to prEN 16963:2016. But the method is very reliable and relatively inexpensive and the method constitu
