1、BS EN 15559:2009ICS 65.080NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBRITISH STANDARDFertilizers Determination ofnitric and ammoniacalnitrogen according toArndThis British Standardwas published under theauthority of the StandardsPolicy and StrategyCommittee on 30 June 2009
2、 BSI 2009ISBN 978 0 580 62387 5Amendments/corrigenda issued since publicationDate CommentsBS EN 15559:2009National forewordThis British Standard is the UK implementation of EN 15559:2009. Itsupersedes DD CEN/TS 15559:2007 which is withdrawn.The UK participation in its preparation was entrusted to Te
3、chnicalCommittee CII/37, Fertilisers 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.Compli
4、ance with a British Standard cannot confer immunityfrom legal obligations.BS EN 15559:2009EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 15559January 2009ICS 65.080 Supersedes CEN/TS 15559:2007 English VersionFertilizers - Determination of nitric and ammoniacal nitrogenaccording to ArndEngrais -
5、Dosage de lazote nitrique et ammoniacal selonArndDngemittel - Bestimmung von Nitrat- undAmmoniumstickstoff nach ArndThis European Standard was approved by CEN on 6 December 2008.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this E
6、uropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the CEN Management Centre or to any CEN member.This European Standard exists in three official versions (Engli
7、sh, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own language and notified to the CEN Management Centre has the same status as theofficial versions.CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cy
8、prus, Czech Republic, 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 United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMI
9、T EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2009 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15559:2009: EBS EN 15559:2009EN 15559:2009 (E) 2 Contents Page Forewo
10、rd 3 1 Scope 4 2 Normative references 4 3 Terms and definitions .4 4 Principle 4 5 Reagents .4 6 Apparatus .6 7 Sampling and sample preparation 11 8 Procedure 11 9 Calculation and expression of the result . 14 10 Test report . 14 Bibliography . 15 BS EN 15559:2009EN 15559:2009 (E) 3 Foreword This do
11、cument (EN 15559:2009) 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 by endorsement, at the latest
12、 by July 2009, and conflicting national standards shall be withdrawn at the latest by July 2009. 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 pate
13、nt rights. This document supersedes CEN/TS 15559:2007. 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 organizations of the following countries a
14、re bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Swe
15、den, Switzerland and the United Kingdom. BS EN 15559:2009EN 15559:2009 (E) 4 1 Scope This European Standard specifies a method for the determination of nitric and ammoniacal nitrogen with reduction according to Arnd (modified for each of the variants a, b and c). The method is applicable to all nitr
16、ogenous fertilizers, including compound fertilizers, in which nitrogen is found exclusively in nitrate form, or in ammoniacal and nitrate form. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cit
17、ed 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 Vocabulary
18、 Part 1: General terms EN 12944-2:1999, Fertilizers and liming materials and soil improvers Vocabulary Part 2: Terms relating to fertilizers EN ISO 3696:1995, Water for analytical laboratory use Specification and test methods (ISO 3696:1987) 3 Terms and definitions For the purposes of this document,
19、 the terms and definitions given in EN 12944-1:1999 and EN 12944-2:1999 apply. 4 Principle Reduction of nitrates and nitrites to ammonia in a neutral aqueous solution by means of a metallic alloy composed of 60 % Cu and 40 % Mg (Arnds alloy) in the presence of magnesium chloride. Distillation of the
20、 ammonia and determination of the yield in a known volume of standard sulfuric acid solution. Titration of the excess acid by means of a standard solution of sodium or potassium hydroxide. 5 Reagents 5.1 General Use only reagents of recognized analytical grade and distilled or demineralized water, f
21、ree from carbon dioxide and all nitrogenous compounds (grade 3 according to EN ISO 3696:1995). 5.2 Diluted hydrochloric acid Mix one volume of concentrated hydrochloric acid solution, (HCl) = 1,18 g/ml, with one volume of water. BS EN 15559:2009EN 15559:2009 (E) 5 5.3 Sulfuric acid (for variant a),
22、c = 0,05 mol/l. 5.4 Sodium or potassium hydroxide solution (for variant a), carbonate free, c = 0,1 mol/l. 5.5 Sulfuric acid (for variant b, see NOTES in 8.2), c = 0,1 mol/l. 5.6 Sodium or potassium hydroxide solution (for variant b, see NOTES in 8.2), carbonate free, c = 0,2 mol/l. 5.7 Sulfuric aci
23、d (for variant c, see NOTES in 8.2), c = 0,25 mol/l. 5.8 Sodium or potassium hydroxide solution (for variant c, see NOTES in 8.2), carbonate free, c = 0,5 mol/l. 5.9 Sodium hydroxide solution, approximately c = 2 mol/l. 5.10 Arnds alloy, powdered so as to pass through a sieve with apertures less tha
24、n 1 mm square. 5.11 Magnesium chloride solution, = 20 %. Dissolve 200 g of magnesium chloride (MgCl2.6H2O) in approximately 600 ml to 700 ml of water in a 1 l flat-bottomed flask. To prevent frothing, add 15 g of magnesium sulfate (MgSO4.7H2O). After dissolution add 2 g of magnesium oxide and a few
25、anti-bump granules of pumice stone and concentrate the suspension to 200 ml by boiling, thus expelling any trace of ammonia from the reagents. Cool, make up the volume to 1 l and filter. 5.12 Indicator solutions 5.12.1 Mixed indicator Solution A: Dissolve 1 g of methyl red in 37 ml of sodium hydroxi
26、de solution c = 0,1 mol/l and make up to 1 l with water. Solution B: Dissolve 1 g of methylene blue in water and make up to 1 l. Mix one volume of solution A with two volumes of solution B. This indicator is violet in acid solution, grey in neutral solution and green in alkaline solution. Use 0,5 ml
27、 (10 drops) of this indicator solution. 5.12.2 Methyl red indicator solution Dissolve 0,1 g of methyl red in 50 ml of 95 % ethanol. Make up to 100 ml with water and filter if necessary. This indicator may be used (4 to 5 drops) instead of that specified in 5.12.1. 5.12.3 Congo red indicator solution
28、 Dissolve 3 g of Congo red in 1 l of warm water and filter if necessary after cooling. This indicator may be used, instead of that specified in 5.12.1.or 5.12.2, in the neutralization of acid extracts before distillation, using 0,5 ml per 100 ml of liquid to be neutralized. 5.13 Anti-bump granules,
29、for example pumice stone, washed in hydrochloric acid and reclaimed. BS EN 15559:2009EN 15559:2009 (E) 6 5.14 Sodium nitrate, p.a. 6 Apparatus 6.1 Distillation apparatus Consisting of a round-bottomed flask of suitable capacity connected to a condenser by means of a splash head. The equipment is mad
30、e of borosilicate glass. NOTE The different types of equipment recommended for this determination are reproduced, showing all the features of construction, in Figures 1, 2, 3 and 4. An automatic distillation apparatus may also be used, provided that the results are statistically equivalent. BS EN 15
31、559:2009EN 15559:2009 (E) 7 Dimensions in millimetres Key 1 round-bottomed, long-necked flask of 1 000 ml capacity 2 distillation tube with a splash head, connected to the condenser by means of a spherical joint (No 18) (the spherical joint for the connection to the condenser may be replaced by an a
32、ppropriate rubber connection) 3 funnel with a polytetrafluoroethylene (PTFE) tap (6) for the addition of sodium hydroxide (the tap may likewise be replaced by a rubber connection with a clip) 4 six-bulb condenser with spherical joint (No 18) at the entrance, and joined at the issue to a glass extens
33、ion tube by means of a small rubber connection (when the connection to the distillation tube is effected by means of a rubber tube, the spherical joint may be replaced by a suitable rubber bung) 5 500 ml flask in which the distillate is collected 6 PTFE-tap a hole Figure 1 Distillation apparatus 1 B
34、S EN 15559:2009EN 15559:2009 (E) 8 Dimensions in millimetres Key 1 round-bottomed, short-necked flask of 1 000 ml capacity with a spherical joint (No 35) 2 distillation tube with a splash head, equipped with a spherical joint (No 35) at the entrance and a spherical joint (No 18) at the issue, connec
35、ted at the side to a funnel with a polytetrafluoroethylene (PTFE) tap (5) for the addition of sodium hydroxide 3 six-bulb condenser with a spherical joint (No 18) at the entrance and joined at the issue to a glass extension tube by means of a small rubber connection 4 500 ml flask in which the disti
36、llate is collected 5 PTFE-tap a enlarged description Figure 2 Distillation apparatus 2 BS EN 15559:2009EN 15559:2009 (E) 9 Dimensions in millimetres Key 1 round-bottomed, long-necked flask of 750 ml or 1 000 ml capacity with, a bell mouth 2 distillation tube with a splash head and a spherical joint
37、(No 18) at the issue 3 elbow tube with a spherical joint (No 18) at the entrance and a drip cone (the connection to the distillation tube may be effected by means of a rubber tube instead of a spherical joint) 4 six-bulb condenser joined at the issue to a glass extension tube by means of a small rub
38、ber connection 5 500 ml flask in which the distillate is collected Figure 3 Distillation apparatus 3 BS EN 15559:2009EN 15559:2009 (E) 10 Dimensions in millimetres Key 1 round-bottomed, long-necked flask of 1 000 ml capacity with a bell mouth 2 distillation tube with a splash head and a spherical jo
39、int (No 18), at the issue, connected at the side to a funnel with a polytetrafluoroethylene (PTFE) tap (5) for the addition of sodium hydroxide (a suitable rubber bung may be used instead of the spherical joint; the tap may be replaced by a rubber connection with an appropriate clip) 3 six-bulb cond
40、enser with a spherical joint (No 18) at the entrance, joined at the issue, by a rubber connection, to a glass extension tube (when the connection to the distillation tube is effected by means of a rubber tube, the spherical joint may be replaced by a suitable rubber bung) 4 500 ml flask for the coll
41、ection of the distillate 5 PTFE-tap Figure 4 Distillation apparatus 4 BS EN 15559:2009EN 15559:2009 (E) 11 6.2 Pipettes, of capacity 10 ml, 20 ml, 25 ml, 50 ml, 100 ml and 200 ml. 6.3 Graduated flask, of capacity 500 ml. 6.4 Rotary shaker, 35 to 40 turns per minute. 7 Sampling and sample preparation
42、 Sampling is not part of the method specified in this Technical Specification. A recommended sampling method is given in EN 1482-1. Sample preparation shall be carried out in accordance with EN 1482-2. 8 Procedure 8.1 Preparation of the solution 8.1.1 General Carry out a solubility test on the sampl
43、e in water at room temperature and in the proportion of 2 % (mass concentration). Weigh to 0,001 g, according to the indications given in Table 1, a quantity of 5 g or 7 g or 10 g of the prepared sample and place it in a 500 ml graduated flask. According to the result of the solubility test, proceed
44、 as follows: 8.1.2 Products completely soluble in water Add to the flask the quantity of water needed to dissolve the sample; shake, and when completely dissolved, make up the volume and mix thoroughly. 8.1.3 Products not completely soluble in water Add to the flask 50 ml of water and then 20 ml of
45、hydrochloric acid (5.2). Shake and leave undisturbed until the evolution of carbon dioxide has ceased. Add 400 ml of water and shake for half an hour with the rotary shaker (6.4). Make up the volume with water, mix and filter through a dry filter into a dry receptacle. 8.2 Analysis of the solution A
46、ccording to the chosen variant, place in the receiving flask the exactly measured quantity of standard sulfuric acid as indicated in Table 1, Table 2 or Table 3. Add the appropriate quantity of chosen indicator solution (5.12.1 or 5.12.2) and finally, sufficient water to give a volume of at least 50
47、 ml. The end of the extension tube of the condenser shall be below the surface of the solution. Using a precision pipette, take, according to Table 1, Table 2 or Table 3, an adequate aliquot of the clear solution. Place it in the distillation flask. BS EN 15559:2009EN 15559:2009 (E) 12 Add sufficien
48、t water to obtain a total volume of about 350 ml (see NOTE 1), 10 g of Arnds alloy (5.10), 50 ml of magnesium chloride solution (5.11) and a few fragments of pumice stone (5.13). Rapidly connect the flask to the distillation apparatus. Heat gently for about 30 min. Then increase the heating to disti
49、l the ammonia. Continue the distillation for about 1 h. After this time, the residue in the flask ought to have a syrupy consistency. When the distillation has finished, lower the receiving flask so that the tip of the condenser extension is above the surface of the liquid. Test the subsequent distillate by means of an appropriate reagent to ensure that all the ammonia is completely distilled. Wash the condenser extension with a little water and titrate the surplus acid with the standard solution of sodium or potassium hydroxide prescribed for the v
