SIST EN ISO 14719:2012

SLOVENSKI STANDARD
SIST EN ISO 14719:2012
01-marec-2012
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)HVVSHNWURIRWRPHWULMVNRPHWRGR]IHQDQWUROLQRP,62
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)
Chemische Analyse von feuerfestem Werkstoff, Glas und Glasuren -
Spektralphotometrische Bestimmung von Eisen(II) und Eisen(III) mit 1,10-Phenanthrolin
(ISO 14719:2011)
Analyse chimique de matériaux réfractaires, du verre et d'émaux - Dosage de Fe2+ et
Fe3+ par la méthode spectrophotométrique en utilisant la 1,10-phénanthroline (ISO
14719:2011)
Ta slovenski standard je istoveten z: EN ISO 14719:2011
ICS:
71.040.40 Kemijska analiza Chemical analysis
81.040.01 Steklo na splošno Glass in general
81.080 Ognjevzdržni materiali Refractories
SIST EN ISO 14719:2012 en,fr
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST EN ISO 14719:2012

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SIST EN ISO 14719:2012


EUROPEAN STANDARD
EN ISO 14719

NORME EUROPÉENNE

EUROPÄISCHE NORM
December 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 matériaux réfractaires, du verre et Chemische Analyse von feuerfestem Werkstoff, Glas und
d'émaux - Dosage de Fe2+ et Fe3+ par la méthode Glasuren - Spektralphotometrische Bestimmung von
spectrophotométrique en utilisant la 1,10-phénanthroline Eisen(II) und Eisen(III) mit 1,10-Phenanthrolin (ISO
(ISO 14719:2011) 14719:2011)
This European Standard was approved 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
standards 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 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, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland,
Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.





EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2011 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 14719:2011: E
worldwide for CEN national Members.

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SIST EN ISO 14719:2012
EN ISO 14719:2011 (E)
Contents Page
Foreword .3

2

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SIST EN ISO 14719:2012
EN ISO 14719:2011 (E)
Foreword
This document (EN ISO 14719:2011) has been prepared by Technical Committee ISO/TC 33 "Refractories" in
collaboration 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 national 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/CENELEC 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,
Lithuania, 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.

3

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SIST EN ISO 14719:2012

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SIST EN ISO 14719:2012

INTERNATIONAL ISO
STANDARD 14719
First edition
2011-12-01

Chemical analysis of refractory material
2
glass and glazes — Determination of Fe
3
and Fe by the spectral photometric
method with 1,10-phenanthroline
Analyse chimique de matériaux réfractaires, du verre et d'émaux —
2 3
Dosage de Fe et Fe par la méthode spectrophotométrique en
utilisant la 1,10-phénanthroline




Reference number
ISO 14719:2011(E)
©
ISO 2011

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SIST EN ISO 14719:2012
ISO 14719:2011(E)

COPYRIGHT PROTECTED DOCUMENT


©  ISO 2011
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any means,
electronic or mechanical, including photocopying and microfilm, without permission in writing from either ISO at the address below or
ISO's member body in the country of the requester.
ISO copyright office
Case postale 56  CH-1211 Geneva 20
Tel. + 41 22 749 01 11
Fax + 41 22 749 09 47
E-mail copyright@iso.org
Web www.iso.org
Published in Switzerland

ii © ISO 2011 – All rights reserved

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SIST EN ISO 14719:2012
ISO 14719:2011(E)
Contents 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
Annex A (informative) Precision . 11
Bibliography . 13

© ISO 2011 – All rights reserved iii

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SIST EN ISO 14719:2012
ISO 14719:2011(E)
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies
(ISO member bodies). The work of preparing International Standards 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, also 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 committees 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 possibility 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.

iv © ISO 2011 – All rights reserved

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SIST EN ISO 14719:2012
INTERNATIONAL STANDARD ISO 14719:2011(E)

Chemical analysis of refractory material glass and glazes —
2 3
Determination of Fe and Fe by the spectral photometric
method with 1,10-phenanthroline
1 Scope
This International Standard specifies a spectral photometric method with 1,10-phenanthroline for the
2 3
quantitative determination of Fe and Fe in 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 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 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, Water 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: Sampling
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-bead 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 definitions given in ISO 26845 apply.
© ISO 2011 – All rights reserved 1

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SIST EN ISO 14719:2012
ISO 14719:2011(E)
4 Principle of Methods A and B
Samples are digested in a mixture of hydrofluoric acid and sulfuric acid. In the presence of a complexing
2
agent, 1,10-phenanthroline, Fe ions form a pink complex. The pink 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 techniquesI. 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-H SO dissolution of the sample is carried out.
2 4
2 3
Methods A and B implement different strategies to avoid oxidation of Fe to Fe during 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 applicable 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 performed 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 µm and stored afterwards in a stoppered sample
bottle in a desiccator.
2 3
The samples shall be dried to constant mass at 110 °C before the determination of Fe /Fe .
Weigh precisely the correct sample amount for the dissolution.
2
NOTE The drying of samples will not change the Fe content in almost all refractory materials; the moisture content
might vary with time.
6 Interferences
2 3 5 3
Interferences in the determination of Fe /Fe can be caused by other polyvalent ions, e.g. As /As ,
5 3
Sb /Sb , 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 for this analysis.
7.1.1.1 Water, according to ISO 3696, at least of Grade 2.
3
7.1.1.2 Sulfuric acid, H SO ,   1,84 g/cm .
2 4
7.1.1.3 Sulfuric acid (1  1).
2 © ISO 2011 – All rights reserved

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SIST EN ISO 14719:2012
ISO 14719:2011(E)
3
7.1.1.4 Hydrofluoric acid, HF,   1,13 g/cm .
7.1.1.5 Hydrofluoric acid, without reducing agents.
Transfer 50 ml of hydrofluoric acid (7.1.1.4) into a platinum dish. Add one drop of 0,02 mol/l KMnO (7.1.1.15)
4
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 (H BO ) to 1 800 ml of water.
3 3
.
7.1.1.7 Hydroxylammonium chloride, NH OH HCl (100 g/l).
2
7.1.1.8 1,10-Phenanthroline solution (5 g/l).
7.1.1.9 Ammonium acetate, CH COONH (approximately 50 % by mass).
3 4
Dissolve 50 g of ammonium acetate in 50 ml of water.
7.1.1.10 Ammonium iron(II) sulfate hexahydrate, Fe(NH ) (SO ) ·6H O.
4 2 4 2 2
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(NH ) (SO ) ·6H O] (7.1.1.10) and transfer to a
4 2 4 2 2
3
500 ml volumetric flask. Dissolve in water, add 8 ml to 10 ml of hydrochloric acid (  1,19 g/cm ), dilute to
volume and mix.
7.1.1.10.2 Iron 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/h to 280 l/h.
3
7.1.1.12 Hydrochloric acid, HCl,   1,19 g/cm .
7.1.1.13 Hydrochloric acid (1  4).
7.1.1.14 Hydrochloric acid (1  12).
7.1.1.15 Potassium permanganate solution, KMnO , 0,02 mol/l (3,160 64 g/l).
4
7.1.2 Apparatus
For solutions that do not contain hydrofluoric acid, ordinary laboratory apparatus 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 used 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.
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SIST EN ISO 14719:2012
ISO 14719:2011(E)
7.1.2.1 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 in ISO 648.
...