1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS EN ISO 14719:2011Chemical analysis of refractorymaterial glass and glazes Determination of Fe2+and Fe3+ by the spectralphotometric method with1,10-phenanthroline (ISO14719:201
2、1)BS EN ISO 14719:2011 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN ISO14719:2011.The UK participation in its preparation was entrusted to TechnicalCommittee RPI/1, Refractory products and materials.A list of organizations represented on this committee can be
3、obtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2012ISBN 978 0 580 70333 1ICS 81.040.01; 81.060.01; 81.080Compliance with a British Standar
4、d cannot confer immunity fromlegal obligations.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 31 January 2012.Amendments issued since publicationDate T e x t a f f e c t e dEUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 14719 Decemb
5、er 2011 ICS 81.080; 81.060.01; 81.040.01 English Version Chemical analysis of refractory material glass and glazes - Determination of Fe2+ and Fe3+ by the spectral photometric method with 1,10-phenanthroline (ISO 14719:2011) Analyse chimique de matriaux rfractaires, du verre et dmaux - Dosage de Fe2
6、+ et Fe3+ par la mthode spectrophotomtrique en utilisant la 1,10-phnanthroline (ISO 14719:2011) Chemische Analyse von feuerfestem Werkstoff, Glas und Glasuren - Spektralphotometrische Bestimmung von Eisen(II) und Eisen(III) mit 1,10-Phenanthrolin (ISO 14719:2011) This European Standard was approved
7、by CEN on 30 November 2011. 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 national st
8、andards may be obtained on application to the CEN-CENELEC 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 and
9、 notified to the CEN-CENELEC 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, Lit
10、huania, 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 2011
11、 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 14719:2011: EBS EN ISO 14719:2011EN ISO 14719:2011 (E) 3 Foreword This document (EN ISO 14719:2011) has been prepared by Technical Committee ISO/TC 33 “Refractories“ in collabora
12、tion with Technical Committee CEN/TC 187 “Refractory products and materials” the secretariat of which is held by BSI. 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 June 2012, and conflicting nat
13、ional standards shall be withdrawn at the latest by June 2012. 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. According to the CEN/CE
14、NELEC 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, Ireland, Italy, Latvia, Lithua
15、nia, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. Endorsement notice The text of ISO 14719:2011 has been approved by CEN as a EN ISO 14719:2011 without any modification. BS EN ISO 14719:2011ISO 14719:2011(E)
16、 ISO 2011 All rights reserved iiiContents Page Foreword iv 1 Scope 1 2 Normative references 1 3 Terms and definitions . 1 4 Principle of Methods A and B 2 5 Sample preparation . 2 6 Interferences 2 7 Sample disintegration and measurement . 2 8 Calculation and expression of results 9 9 Test report 10
17、 Annex A (informative) Precision 11 Bibliography 13 BS EN ISO 14719:2011ISO 14719:2011(E) iv ISO 2011 All rights reservedForeword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International S
18、tandards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison with ISO, als
19、o take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2. The main task of technical committe
20、es is to prepare International Standards. Draft International Standards adopted by the technical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote. Attention is drawn to the possi
21、bility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. ISO 14719 was prepared by Technical Committee ISO/TC 33, Refractories. BS EN ISO 14719:2011INTERNATIONAL STANDARD ISO 14719:2011(E)
22、ISO 2011 All rights reserved 1Chemical analysis of refractory material glass and glazes Determination of Fe2and Fe3by the spectral photometric method with 1,10-phenanthroline 1 Scope This International Standard specifies a spectral photometric method with 1,10-phenanthroline for the quantitative det
23、ermination of Fe2and Fe3in oxidic raw and basic materials for ceramics, glass and glazes, e.g. feldspar, kaolinites, clay, limestone, quartz refractory materials. This International Standard could be extended to other aluminosilicate materials, providing that uncertainty data is produced to support
24、it. However, there might be problems in the decomposition of high-purity alumina and chrome ore samples. The method is not suitable for reduced materials, such as silicon carbide, graphite-magnesia, etc. 2 Normative references The following referenced documents are indispensable for the application
25、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. ISO 648, Laboratory glassware Single-volume pipettes ISO 1042, Laboratory glassware One-mark volumetric flasks ISO 3696, W
26、ater for analytical laboratory use Specification and test methods ISO 5022, Shaped refractory products Sampling and acceptance testing ISO 6286, Molecular absorption spectrometry Vocabulary General Apparatus ISO 8656-1, Refractory products Sampling of raw materials and unshaped products Part 1: Samp
27、ling scheme ISO 10725, Acceptance sampling plans and procedures for the inspection of bulk materials ISO 11648-2, Statistical aspects of sampling from bulk materials Part 2: Sampling of particulate materials ISO 12677, Chemical analysis of refractory products by X-ray fluorescence (XRF) Fused cast-b
28、ead method ISO 26845, Chemical analysis of refractories General requirements for wet chemical analysis, atomic absorption spectrometry (AAS) and inductively coupled plasma atomic emission spectrometry (ICP-AES) methods 3 Terms and definitions For the purposes of this document, the terms and definiti
29、ons given in ISO 26845 apply. BS EN ISO 14719:2011ISO 14719:2011(E) 2 ISO 2011 All rights reserved4 Principle of Methods A and B Samples are digested in a mixture of hydrofluoric acid and sulfuric acid. In the presence of a complexing agent, 1,10-phenanthroline, Fe2ions form a pink complex. The pink
30、 complex is measured photometrically at 510 nm in an aqueous solution. Quantitative results are obtained by calibration with reference solutions. The sum of the determination of both iron species corresponds to the total iron content. This International Standard provides two sample dissolution techn
31、iquesI. In Method A, ten times more sample (500 mg) is necessary than for Method B (20 mg to 30 mg). As a consequence, the amount of reagents needed are reduced for Method B. In both methods, a HF-H2SO4dissolution of the sample is carried out. Methods A and B implement different strategies to avoid
32、oxidation of Fe2to Fe3during the sample dissolution and measurement: while in Method A the samples react in an air- and light-tight reaction vessel with nitrogen, in Method B the solution is stabilized with nitrilotriacetic acid in simple polystyrene cuvettes cooled by ice. Both methods are applicab
33、le for the full range of materials covered by the scope of this International Standard. For samples which appear more heterogeneous, a higher sample mass for the preparation may lead to more reproducible results. In this case, Method A shall be applied. 5 Sample preparation The sampling shall be per
34、formed in accordance with ISO 5022 or ISO 8656-1 with reference, where appropriate, to ISO 10725 and ISO 11648-2. The sample shall be ground to a particle size less than 63 m and stored afterwards in a stoppered sample bottle in a desiccator. The samples shall be dried to constant mass at 110 C befo
35、re the determination of Fe2/Fe3. Weigh precisely the correct sample amount for the dissolution. NOTE The drying of samples will not change the Fe2content in almost all refractory materials; the moisture content might vary with time. 6 Interferences Interferences in the determination of Fe2/Fe3can be
36、 caused by other polyvalent ions, e.g. As5/As3, Sb5/Sb3, etc. The formation of an insoluble precipitate, e.g. lead and barium sulfate, may also interfere in the determination. 7 Sample disintegration and measurement 7.1 Method A 7.1.1 Reagents Reagents of a recognized analytical grade shall be used
37、for this analysis. 7.1.1.1 Water, according to ISO 3696, at least of Grade 2. 7.1.1.2 Sulfuric acid, H2SO4, 1,84 g/cm3. 7.1.1.3 Sulfuric acid (1 1). BS EN ISO 14719:2011ISO 14719:2011(E) ISO 2011 All rights reserved 37.1.1.4 Hydrofluoric acid, HF, 1,13 g/cm3. 7.1.1.5 Hydrofluoric acid, without reduc
38、ing agents. Transfer 50 ml of hydrofluoric acid (7.1.1.4) into a platinum dish. Add one drop of 0,02 mol/l KMnO4(7.1.1.15) solution. Heat on a steam bath until the permanganate is reduced. Cool for use and store in a polyethylene bottle. 7.1.1.6 Boric acid solution. Add 90 g of boric acid (H3BO3) to
39、 1 800 ml of water. 7.1.1.7 Hydroxylammonium chloride, NH2OH.HCl (100 g/l). 7.1.1.8 1,10-Phenanthroline solution (5 g/l). 7.1.1.9 Ammonium acetate, CH3COONH4(approximately 50 % by mass). Dissolve 50 g of ammonium acetate in 50 ml of water. 7.1.1.10 Ammonium iron(II) sulfate hexahydrate, Fe(NH4)2(SO4
40、)26H2O. 7.1.1.10.1 Iron stock solution (1 ml 1 mg Fe). Weigh 3,510 8 g of ammonium iron(II) sulfate hexahydrate Fe(NH4)2(SO4)26H2O (7.1.1.10) and transfer to a 500 ml volumetric flask. Dissolve in water, add 8 ml to 10 ml of hydrochloric acid ( 1,19 g/cm3), dilute to volume and mix. 7.1.1.10.2 Iron
41、standard solution (1 ml 0,01 mg Fe). Dilute 10 ml of the iron stock solution to 1 000 ml in a volumetric flask with deionized water. 7.1.1.11 Nitrogen gas, white spot (high quality). The gas cylinder should be provided with a two-stage reducing valve and a gas-flow regulator for a flow rate of 28 l/
42、h to 280 l/h. 7.1.1.12 Hydrochloric acid, HCl, 1,19 g/cm3. 7.1.1.13 Hydrochloric acid (1 4). 7.1.1.14 Hydrochloric acid (1 12). 7.1.1.15 Potassium permanganate solution, KMnO4, 0,02 mol/l (3,160 64 g/l). 7.1.2 Apparatus For solutions that do not contain hydrofluoric acid, ordinary laboratory apparat
43、us and the usual laboratory glassware made from borosilicate glass and complying with the requirements of relevant International Standards shall be used. For solutions containing hydrofluoric acid or any acidic fluoride, plastic apparatus shall be used. Graduated plastic graduated flasks shall be us
44、ed for sample stock solutions and calibration standards, etc. Beakers, storing bottles, volumetric flasks and pipettes shall be prepared by filling them to 90 % of the overflow capacity with hydrochloric acid (7.1.1.14) overnight. After the soaking, they shall be washed thoroughly with water. BS EN
45、ISO 14719:2011ISO 14719:2011(E) 4 ISO 2011 All rights reserved7.1.2.1 Analytical balance, capable of reading to the nearest 0,1 mg. 7.1.2.2 Volumetric flasks, complying with the requirements of class A in ISO 1042. 7.1.2.3 Pipettes, of suitable capacities complying with the requirements of class A i
46、n ISO 648. 7.1.2.4 Magnetic stirrer. 7.1.2.5 Molecular absorption spectrometer, conforming to the requirements of ISO 6286. 7.1.2.6 Optical cells, as recommended by the spectrometer manufacturer. 7.1.2.7 Hotplate. 7.1.2.8 Reaction vessel. Plastic or polytetrafluoroethylene (PTFE) bottle or beaker of
47、 250 ml capacity. The vessel will be used to exclude air (oxygen) when reacting the sample with the reagents. The vessel can be fitted with a rubber stopper, as shown in Figure 1, or the vessel can be a beaker with the lip removed and the bottom of another container placed on top, with the appropria
48、te openings for introduction of purge gas, reagents, and vent tubing. In order to exclude light, the vessel shall be covered with black paint on the surface. The vessel comprises the components described in 7.1.2.8.1 to 7.1.2.8.5. 7.1.2.8.1 Plastic or TFE-fluorocarbon bottle or beaker, of 250 ml cap
49、acity. 7.1.2.8.2 Plastic tube, used to introduce the purge gas into the vessel. It is advisable to use a connection between the plastic tubing and the gas cylinder that will allow it to be easily connected and disconnected. 7.1.2.8.3 Plastic powder funnel, that allows for the addition of the reagents to the sample without interfering with the purged atmosphere in the vessel. 7.1.2.8.4 Vent tube, to allow the escape of gas when reagents are being added through the powder funnel. I
