SIST EN ISO 4934:2004

SLOVENSKI STANDARD
01-junij-2004
1DGRPHãþD
SIST EN 24934:1997
Steel and iron - Determination of sulfur content - Gravimetric method (ISO
4934:2003)
Steel and iron - Determination of sulfur content - Gravimetric method (ISO 4934:2003)
Stahl und Eisen - Bestimmung des Schwefelgehaltes - Gravimetrisches Verfahren (ISO
4934:2003)
Aciers et fontes - Dosage de soufre - Méthode gravimétrique (ISO 4934:2003 )
Ta slovenski standard je istoveten z: EN ISO 4934:2003
ICS:
77.040.30 Kemijska analiza kovin Chemical analysis of metals
77.080.01 Železne kovine na splošno Ferrous metals in general
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EUROPEAN STANDARD
EN ISO 4934
NORME EUROPÉENNE
EUROPÄISCHE NORM
December 2003
ICS 77.080.01 Supersedes EN 24934:1989
English version
Steel and iron - Determination of sulfur content - Gravimetric
method (ISO 4934:2003)
Aciers et fontes - Dosage de soufre - Méthode Stahl und Eisen - Bestimmung des Schwefelgehaltes -
gravimétrique (ISO 4934:2003 ) Gravimetrisches Verfahren (ISO 4934:2003)
This European Standard was approved by CEN on 10 December 2003.
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 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 Management Centre has the same status as the official
versions.
CEN members are the national standards bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece,
Hungary, Iceland, Ireland, Italy, Luxembourg, Malta, Netherlands, Norway, Portugal, Slovakia, Spain, Sweden, Switzerland and United
Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
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© 2003 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 4934:2003 E
worldwide for CEN national Members.

CORRECTED  2004-03-03
Foreword
Le présent document (EN ISO 4934:2003) a été élaboré par le Comité Technique ISO/TC 17
"Acier" en collaboration avec le Comité Technique ECISS/TC 20 "Analyses chimiques" dont le
secrétariat est tenu par le SIS.
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 2004, and conflicting national
standards shall be withdrawn at the latest by June 2004.
This document supersedes EN 24934:1989.
According to the CEN/CENELEC Internal Regulations, the national standards organizations of
the following countries are bound to implement this European Standard: Austria, Belgium, Czech
Republic, Denmark, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy,
Luxembourg, Malta, Netherlands, Norway, Portugal, Slovakia, Spain, Sweden, Switzerland and
the United Kingdom.
Endorsement notice
The text of ISO 4934:2003 has been approved by CEN as EN ISO 4934:2003 without any
modifications.
NOTE Normative references to International Standards are listed in Annex ZA (normative).
Annex ZA
(normative)
Normative references to international publications
with their relevant European publications
This European Standard incorporates by dated or undated reference, provisions from other
publications. These normative references are cited at the appropriate places in the text and the
publications are listed hereafter. For dated references, subsequent amendments to or revisions of
any of these publications apply to this European Standard only when incorporated in it by
amendment or revision. For undated references the latest edition of the publication referred to
applies (including amendments).
NOTE Where an International Publication has been modified by common modifications, indicated
by (mod.), the relevant EN/HD applies.
Publication Year Title EN Year
ISO 3696 1987 Water for analytical laboratory use - EN ISO 3696 1995
Specification and test methods
ISO 14284 1996 Steel and iron - Sampling and preparation EN ISO 14284 2002
of samples for the determination of
chemical composition
INTERNATIONAL ISO
STANDARD 4934
Second edition
2003-12-15
Steel and iron — Determination of sulfur
content — Gravimetric method
Aciers et fontes — Dosage du soufre — Méthode gravimétrique

Reference number
ISO 4934:2003(E)
©
ISO 2003
ISO 4934:2003(E)
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ii ISO 2003 – All rights reserved

ISO 4934:2003(E)
Contents Page
1 Scope . 1
2 Normative references . 1
3 Principle . 1
4 Reagents . 2
5 Apparatus . 3
6 Sampling . 4
7 Procedure . 4
8 Expression of results . 6
9 Test report . 7
Annex A (informative) Additional information on international cooperative tests . 9
Annex B (informative) Graphical representation of precision data . 10
©
ISO 2003 – All rights reserved iii

ISO 4934:2003(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.
ISO4934 was prepared by Technical Committee ISO/TC17, Steel, Subcommittee SC1, Methods of
determination of chemical composition.
This second edition cancels and replaces the first edition (ISO 4934:1980), which has been technically revised.
©
iv ISO 2003 – All rights reserved

INTERNATIONAL STANDARD ISO 4934:2003(E)
Steel and iron — Determination of sulfur content — Gravimetric
method
1Scope
This International Standard specifies a gravimetric method for the determination of the sulfur content in steels
and iron, excluding steels containing selenium. The method is particularly suitable as a reference method for
the standardization of samples on which certified standard values are to be established.
The method is applicable to a sulfur content between 0,003 % (mass fraction) and 0,35 % (mass fraction).
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 565, Test sieves — Metal wire cloth, perforated metal plate and electroformed sheet — Nominal sizes of
openings
ISO 3696, Water for analytical laboratory use — Specification and test methods
ISO 5725-1, Accuracy (trueness and precision) of measurement methods and results — Part 1: General
principles and definitions
ISO 5725-2, Accuracy (trueness and precision) of measurement methods and results — Part 2: Basic method
for the determination of repeatability and reproducibility of a standard measurement method
ISO 5725-3, Accuracy (trueness and precision) of measurement methods and results — Part 3: Intermediate
measures of the precision of a standard measurement method
ISO 14284, Steel and iron — Sampling and preparation of samples for the determination of chemical
composition
3 Principle
Dissolution of a test portion in dilute nitric acid in the presence of bromine, or in the mixed acid of nitric acid and
hydrochloric acid in the presence of bromine (with the aid of an appropriate device to prevent sulfur losses).
Addition of perchloric acid and evaporation of the solution until white fumes of perchloric acid are evolved.
Filtration of the solution and removal of the dehydrates of silicon, tungsten, niobium,etc.
Addition of a determined quantity of sulfate ions to aid precipitation.
Chromatographic separation of the sulfate ions from the test solution by adsorption on an alumina column, and
elution using an ammonium hydroxide solution.
Precipitation of the sulfate ions as barium sulfate under controlled conditions and filtering, washing, heating and
weighing.
©
ISO 2003 – All rights reserved 1

ISO 4934:2003(E)
4Reagents
During the analysis, use only reagents of recognized analytical grade and only grade 2 water as specified in
ISO 3696.
4.1 Aluminium oxide (alumina, Al O ), prepared for chromatography, of particle size corresponding to a
2 3
sieve mesh size of 75µm to 150µm (supplementary series R 40/3 of ISO 565)
Alumina designated alkaline, neutral or acid may be used.
Place approximately 200 g of the dry alumina in a 400 ml beaker containing 300 ml of water and place the
beaker in a sink. Insert a glass tube having a bore of 5mm, such that it extends to the bottom of the beaker and
connect the tube to a water supply. Adjust the water flow so that the suspended fine material overflows the rim
of the beaker. Continue this treatment until all the fine material, which does not settle within 1 min of stopping
the water flow, is removed.
Pour off the supernatant liquid from the coarser material, add the hydrochloric acid (4.5) in an amount sufficient
to cover the alumina; stir and allow to stand for not less than 12 h. Pour off the hydrochloric acid and wash the
alumina with water as described in the second paragraph.
For preparation of the column, make a slurry of the washed alumina and the hydrochloric acid solution (4.8).
4.2 Bromine (Br ), min 99 % (mass fraction)
4.3 Nitric acid (HNO), ρ=approximately 1,40 g/ml
4.4 Nitric acid (HNO ), ρ= approximately 1,40 g/ml, diluted 1+ 1
4.5 Hydrochloric acid (HCl), ρ= approximately 1,19 g/ml
ρ= 1,19 g/ml 1+ 1
4.6 Hydrochloric acid (HCl), approximately , diluted
4.7 Hydrochloric acid (HCl), ρ= approximately 1,19 g/ml, diluted 1+ 9
4.8 Hydrochloric acid (HCl), ρ= approximately 1,19 g/ml, diluted 1+ 19
4.9 Perchloric acid (HClO), ρ=approximately 1,54 g/ml
NOTE If this reagent is shown to have a high sulfate content, this may be removed by passing the reagent through the
adsorption column (5.4).
4.10 Perchloric acid (HClO ), ρ= approximately 1,54 g/ml, diluted 1+ 49
4.11 Acid mixture
Mix hydrochloric acid (4.5) and nitric acid (4.3) in proportions liable to ensure total solubility of the samples. This
mixture should be freshly prepared as required.
NOTE Generally, aqua regia can be used. For some samples, the proportion of hydrochloric acid and nitric acid can be
adjusted.
4.12 Ammonium hydroxide (NHOH), ρ=approximately 0,90 g/ml
4.13 Ammonium hydroxide (NH OH), ρ= approximately 0,90 g/ml, diluted 1+ 19
4.14 Ammonium hydroxide (NH OH), ρ= approximately 0,90 g/ml, diluted 1+ 99
4.15 Sulfuric acid (H SO ), solution corresponding to approximately 48 mg/l of sulfur
2 4
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2 ISO 2003 – All rights reserved

ISO 4934:2003(E)
Add 2,8 ml of sulfuric acid, ρ= approximately 1,84 g/ml, to about 500 ml of water. Dilute to 1 000 ml and mix.
Take 30 ml of this solution, dilute to 1 000 ml and mix.
4.16 Barium chloride dihydrate (BaCl ·2HO), 1,22 g/lsolution
2 2
Dissolve 1,22 g of barium chloride dihydrate (BaCl ·2H O) in water, dilute to 1 000 ml and mix. Filter the
2 2
solution through close texture filter paper just before use.
1 ml of this solution is equivalent to approximately 0,16 mg of sulfur.
4.17 Methyl orange (C H N NaOS), 0,50 g/lsolution
14 14 3 3
ρ= 1,05 g/ml
4.18 Glacial acetic acid (CHCOOH), approximately
4.19 Hydrogen peroxide (H O), ρ=approximately 1,10 g/ml
2 2
5 Apparatus
Use normal laboratory apparatus.
5.1 Analytical balance, calibrated with nationally or internationally traceable mass, to provide measurement
traceability
5.2 Conical flask, of capacity 1 000
...