1、December 2007DEUTSCHE NORM English price group 12No part of this standard 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 81.080!$JI“1398838www
2、.din.deDDIN EN ISO 21587-2Chemical analysis of aluminosilicate refractory products(alternative to the X-ray fluorescence method) Part 2: Wet chemical analysis (ISO 21587-2:2007)English version of DIN EN ISO 21587-2:2007-12Chemische Analyse feuerfester Erzeugnisse aus Alumosilicat(Alternative zum Rnt
3、genfluoreszenzverfahren) Teil 2: Nasschemische Analyse (ISO 21587-2:2007)Englische Fassung DIN EN ISO 21587-2:2007-12supersedesDIN EN 955-2:1995-06www.beuth.de21587-1:2007-12,Together withDIN EN ISODocument comprises 24 pagesDIN EN ISO 21587-2:2007-12 2 National foreword This standard has been publi
4、shed in accordance with a decision taken by Technical Committee CEN/TC 187 “Refractory products and materials” (Secretariat: BSI, United Kingdom) to adopt, without alteration, International Standard ISO 21587-2:2007 as a European Standard. ISO 21587-2 was prepared by Technical Committee ISO/TC 33 “R
5、efractories”. The responsible German body involved in its preparation was the Normenausschuss Materialprfung (Materials Testing Standards Committee), Technical Committee NA 062-02-61 AA Chemische Analyse von oxidischen Roh- und Werkstoffen. The DIN Standards corresponding to the International Standa
6、rds referred to in clause 2 of the EN are as follows: ISO 21587-1 DIN EN ISO 21587-1 ISO 26845 DIN EN ISO 26845 Amendments This standard differs from DIN EN 955-2:1995-06 as follows: a) The standard has been split into three parts. b) The standard has been completely revised taking into account the
7、current chemical analysis and environmental aspects. Previous editions DIN 51070: 1957-04 DIN 51070-8: 1966-02 DIN 51070-1: 1966-02 DIN 51070-9: 1966-02 DIN 51070-2: 1966-02 DIN 51071: 1957-05 DIN 51070-3: 1966-02 DIN 51077-1: 1972-04 DIN 51070-4: 1966-02 DIN 51077-2: 1972-04 DIN 51070-5: 1966-02 DI
8、N 51077-3: 1972-04 DIN 51070-6: 1966-02 DIN 51081: 1979-07 DIN 51070-7: 1966-02 DIN EN 955-2: 1995-06 National Annex NA (informative) Bibliography DIN EN ISO 21587-1, Chemical analysis of aluminosilicate refractory products (alternative to the X-ray fluorescence method) Part 1: Apparatus, reagents,
9、dissolution and gravimetric silica DIN EN ISO 26845, Chemical analysis of refractories General requirements for wet chemical analysis, AAS and ICP methods EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN ISO 21587-2September 2007ICS 81.080 Supersedes EN 955-2:1995 English VersionChemical analysis o
10、f aluminosilicate refractory products(alternative to the X-ray fluorescence method) - Part 2: Wetchemical analysis (ISO 21587-2:2007)Analyse chimique des produits rfractairesdaluminosilicates (mthode alternative la mthode parfluorescence de rayons X) - Partie 2: Mthodes danalysechimique par voie hum
11、ide (ISO 21587-2:2007)Chemische Analyse feuerfester Erzeugnisse ausAlumosilicat (Alternative zumRntgenfluoreszenzverfahren) - Teil 2: NasschemischeAnalyse (ISO 21587-2:2007)This European Standard was approved by CEN on 13 September 2007.CEN members are bound to comply with the CEN/CENELEC Internal R
12、egulations which stipulate the conditions for giving this EuropeanStandard 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
13、 European Standard exists in three official versions (English, 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
14、national standards bodies of 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, Sweden, Switzerland an
15、d United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2007 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN ISO 21587-
16、2:2007: EContents Page 2 EN ISO 21587-2:2007 (E) Foreword .3 1 Scope .4 2 3 4 Determination of aluminium oxide 6 5 Determination of iron(III) oxide 8 6 7 8 Determination of calcium oxide . 13 9 Determination of magnesium oxide . 14 10 Determination of sodium oxide by flame photometry . 15 11 Determi
17、nation of potassium oxide by flame photometry 17 12 Determination of chromium(III) oxide using diphenylcarbazide . 17 13 Determination of zirconium oxide by Xylenol orange 19 14 Determination of phosphorus(V) oxide by molybdenum blue 20 15 Test report 22 method 12 Determination of titanium(IV) oxide
18、 . 10 Determination of manganese(II) oxide by permanganate absorption spectrophotometric Determination of residual silicon(IV) oxide in solution 5 Normative references .4 Foreword The text of ISO 21587-2:2007 has been prepared by Technical Committee ISO/TC 33 “Refractories” of the International Orga
19、nization for Standardization (ISO) and has been taken over as EN ISO 21587-2:2007 by 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 ident
20、ical text or by endorsement, at the latest by March 2008, and conflicting national standards shall be withdrawn at the latest by March 2008. This document supersedes EN 955-2:1995. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are
21、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, Sweden
22、, Switzerland and United Kingdom. Endorsement notice The text of ISO 21587-2:2007 has been approved by CEN as EN ISO 21587-2:2007 without any modifications. 3 EN ISO 21587-2:2007 (E) 1 Scope This part of ISO 21587 specifies traditional (“wet“) methods for the chemical analysis of aluminosilicate ref
23、ractory products and raw materials. The methods are applicable to the determination of the following: silicon(IV) oxide (SiO2) aluminium oxide (Al2O3) iron(III) oxide (total ir on oxide calculated as Fe2O3) titanium(IV) oxide (TiO2) manganese(II) oxide (MnO) calcium oxide (CaO) magnesium oxide (MgO)
24、 sodium oxide (Na2O) potassium oxide (K2O) chromium(III) oxide (Cr2O3) zirconium oxide (ZrO2) phosphorous(V) oxide (P2O5) This part of ISO 21587 gives alternatives to the X-ray fluorescence (XRF) method given in ISO 12677:2003, Chemical analysis of refractory products by XRF Fused cast bead method.
25、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 (including any amendments) applies. ISO 21587-1:2007, Chemical
26、 analysis of aluminosilicate refractory products (alternative to the X-ray fluorescence method) Part 1: Apparatus, reagents, dissolution and gravimetric silica ISO 26845, Chemical analysis of refractories General requirements for wet chemical analysis, atomic absorption spectrometry and inductively
27、coupled plasma methods 4 EN ISO 21587-2:2007 (E) 3 Determination of residual silicon(IV) oxide in solution 3.1 Principle An aliquot portion of the stock solution (S1) or (S1), after pH adjustment, is treated with ammonium molybdate and the silicomolybdate is reduced to yield molybdenum blue, the abs
28、orbance of which is measured. The sum of this residual silicon(IV) oxide in solution plus the mass of silicon(IV) oxide (m1 m2) derived in ISO 21587-1:2007, 4.2.2.3 or 4.2.3.3, gives the total silicon(IV) oxide content. 3.2 Procedure This determination should be commenced with little delay after the
29、 stock solution (S1) or (S1) is prepared, as prolonged standing can allow polymerization of silica to occur, leading to low results. Transfer 10 ml of stock solution (S1) or (S1) obtained in 4.2.2.3 or 4.2.3.3 of ISO 21587-1:2007 to a 100 ml plastic beaker, and add 2 ml of hydrofluoric acid (1+9), m
30、ix with a plastic rod and allow to stand for 10 min. Then add 50 ml of boric acid solution. Add 2 ml of ammonium molybdate solution while mixing at a temperature of 25 C, and allow to stand for 10 min. Add 5 ml of L(+)-tartaric acid solution while stirring, and after 1 min add to it 2 ml of L(+)-asc
31、orbic acid solution. Transfer the solution to a 100 ml volumetric flask, dilute to the mark with water, mix, and allow to stand for 60 min. Measure the absorbance of the solution in a 10 mm cell at a wavelength of 650 nm using water as the reference. 3.3 Plotting the calibration graph Transfer 0, 2,
32、 4, 6, 8 and 10 ml aliquot portions (0 mg to 0,4 mg as silicon(IV) oxide) of dilute standard silicon(IV) oxide solution (SiO20,04 mg/ml) into several 100 ml plastic beakers, and to each add 10 ml of blank solution (B1) or (B1) obtained in 4.2.2.4 or 4.2.3.4 of ISO 21587-1:2007. Treat these solutions
33、 and measure the absorbance as given in 3.2, and plot the absorbances against the amounts of silicon(IV) oxide. Prepare the calibration graph by adjusting the curve so that it passes through the point of origin. 3.4 Calculation Calculate the mass fraction of silicon(IV) oxide, wSiO2, as a percentage
34、, using the following equation, with the absorbances obtained by the procedure in 3.2 and the plotting of the calibration graph by the procedure in 3.3. ()()212 3 4SiO50010100mm mmwm+= (1) where m1is the mass, in g, from 4.2.2.3 or 4.2.3.3 of ISO 21587-1:2007; m2is the mass, in g, from 4.2.2.3 or 4.
35、2.3.3 of ISO 21587-1:2007; m3is the mass, in g, of silicon(IV) oxide in the aliquot portion of stock solution (S1) or (S1) as applicable; m4is the mass, in g, of silicon(IV) oxide in the aliquot portion of blank solution (B1) or (B1) as applicable; m is the mass, in g, of the test portion from 4.2.2
36、.2 or 4.2.3.2 of ISO 21587-1:2007. 5 EN ISO 21587-2:2007 (E) 4 Determination of aluminium oxide 4.1 General The determination of titanium(IV) oxide is carried out using one of the following methods: a) separation by cupferron-CyDTA-zinc back titration method; b) CyDTA-zinc back titration method (wit
37、hout separation method). 4.2 Separation by cupferron-CyDTA-zinc back titration method 4.2.1 Principle Hydrochloric acid is added to an aliquot portion of stock solution (S1) or (S1), obtained in 4.2.2.3 or 4.2.3.3 of ISO 21587-1:2007, to adjust the acidity. Iron, titanium, manganese and zirconium ar
38、e separated from the solution by solvent extraction with cupferron solution and the precipitate removed by dissolution in chloroform. The organic phase is discarded. Excess standard volumetric CyDTA solution is added to the aqueous solution after adjusting the pH with ammonia solution, and a chelate
39、 compound of aluminium CyDTA is formed. The pH is further adjusted by the addition of ammonium acetate buffer solution and an equivalent volume of ethanol is added to the solution. The amount of excess CyDTA is determined by back-titration with standard volumetric zinc solution using dithizone as an
40、 indicator and the content of aluminium oxide calculated. 4.2.2 Procedure Transfer a 100 ml aliquot portion of the stock solution (S1) or (S1), obtained in 4.2.2.3 or 4.2.3.3 of ISO 21587-1:2007, to a 500 ml separating funnel and add 20 ml of hydrochloric acid (concentrated) To the solution, add 20
41、ml of chloroform and 10 ml of cupferron solution. Stopper the funnel and shake vigorously. Release the pressure in the funnel by carefully removing the stopper and rinse the stopper and neck of the funnel with a little water. Allow the layers to separate and withdraw the chloroform layer. Confirm th
42、at extraction is complete by checking that the addition of a few drops of the cupferron solution to the aqueous solution does not produce a permanent coloured precipitate. Add further 10 ml portions of the chloroform and repeat the extraction until the chloroform layer is colourless. Wash the stem o
43、f the funnel, inside and out, with chloroform, using a polyethylene wash bottle. Discard the chloroform extracts; do not allow them to dry as there can be an explosion risk. Transfer the aqueous solution and washings from the funnel into a 1 l conical flask. Add a few drops of bromophenol blue indic
44、ator and ammonia solution (concentrated) until the solution is just alkaline. Re-acidify quickly with hydrochloric acid (concentrated) and add 5 to 6 drops in excess. Cool to room temperature. Add sufficient standard volumetric CyDTA solution c(CyDTA) = 0,05 mol/l to combine with the aluminium oxide
45、 present, and a few millilitres in excess. NOTE 1 1 ml of standard volumetric CyDTA solution c(CyDTA) = 0,05 mol/l is equivalent to 1,275 % Al203for a 100 ml aliquot portion. Add ammonium acetate buffer solution until the indicator turns blue, followed by 10 ml in excess. Add a volume of the ethanol
46、 equal to the total volume of the solution. If sulfates are precipitated by the alcohol, add just enough water to re-dissolve them. Add 20 ml of hydroxyammonium chloride and 1 ml to 2 ml of dithizone indicator, and titrate with standard volumetric zinc solution c(Zn) = 0,05 mol/l from green to the f
47、irst appearance of a permanent pink colour. NOTE 2 The end point is often improved by the addition of a little naphthol green B solution (1 g/l) to eliminate any pink colour which can be formed in the solution on addition of the indicator. 4.2.3 Blank test Transfer an aliquot portion of blank soluti
48、on (B1) or (B1) obtained in 4.2.2.4 or 4.2.3.4 of ISO 21587-1:2007 and carry out the procedure given in 4.2.2. Use the same volumes of the aliquot portion of blank solution (B1) or (B1) and standard volumetric CyDTA solution c(CyDTA) = 0,05 mol/l as those for the corresponding stock solution (S1) or
49、 (S1). 6 EN ISO 21587-2:2007 (E) 4.2.4 Calculation Calculate the mass fraction of aluminium oxide in the sample as follows. If the standard volumetric CyDTA solution c(CyDTA) = 0,05 mol/l is not exactly 0,05 mol/l, calculate the equivalent volume of standard volumetric CyDTA solution. Calculate the mass fraction of aluminium oxide, wAl2O3, as a percentage, using the equation ()23Al O 1w 1,275 VV= (2) where V is the volume of standard volumetric CyDTA solution c(CyDTA) = 0,05 mol/l added, in ml; V1is the
