BRITISH STANDARD

Chemical analysis of
ferrous materials
Determination of
arsenic in steel and
iron
Spectrophotometric
method

The European Standard EN 10212:1995 has the status of a

British Standard

ICS 71.040.40

BS EN
10212:1996

BS EN 10212:1996

Committees responsible for this

British Standard
The preparation of this British Standard was entrusted to Technical
Committee ISE/18, Sampling and analysis of iron and steel, upon which the
following bodies were represented:
BCIRA
British Iron and Steel Producers Association
Ministry of Defence
Welding Institute

This British Standard, having

been prepared under the
direction of the Engineering
Sector Board, was published
under the authority of the
Standards Board and comes
into effect on
15 February 1996
BSI 11-1999
The following BSI references
relate to the work on this
standard:
Committee reference ISE/18
Draft for comment 91/38468 DC
ISBN 0 580 25440 2

Amendments issued since publication

Amd. No.

Date

Comments

BS EN 10212:1996

Contents
Committees responsible
National foreword
Foreword
Text of EN 10212
List of references

BSI 11-1999

Page
Inside front cover
ii
2
3
Inside back cover

BS EN 10212:1996

National foreword
This British Standard has been prepared by Technical Committee ISE/18 and is
the English language version of EN 10212:1995, Chemical analysis of ferrous
materials Determination of arsenic in steel and iron Spectrophotometric
method, published by the European Committee for Standardization (CEN). It was
produced as a result of international discussions in which the United Kingdom
took an active part.
A British Standard does not purport to include all the necessary provisions of a
contract. Users of British Standards are responsible for their correct application.
Compliance with a British Standard does not of itself confer immunity
from legal obligations.

Summary of pages
This document comprises a front cover, an inside front cover, pages i and ii,
the EN title page, pages 2 to 8, an inside back cover and a back cover.
This standard has been updated (see copyright date) and may have had
amendments incorporated. This will be indicated in the amendment table on the
inside front cover.
ii

BSI 11-1999

EUROPEAN STANDARD

EN 10212

NORME EUROPENNE
March 1995

EUROPISCHE NORM
ICS 71.040.40

Descriptors: Iron and steel products, steels, cast iron, chemical analysis, determination of content, arsenic, spectrophotometric analysis

English version

Chemical analysis of ferrous materials

Determination of arsenic in steel and iron
Spectrophotometric method

Analyse chimique des matriaux

sidrurgiques Dosage de larsenic dans les
aciers et les fontes Mthode
spectrophotomtrique

Chemische Analyse von Eisenwerkstoffen

Bestimmung von Arsen in Stahl und Eisen
mittels Spektralphotometrie

This European Standard was approved by CEN on 1995-02-06. 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 Central Secretariat 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
Central Secretariat has the same status as the official versions.
CEN members are the national standards bodies of Austria, Belgium,
Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy,
Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and
United Kingdom.

CEN
European Committee for Standardization
Comit Europen de Normalisation
Europisches Komitee fr Normung
Central Secretariat: rue de Stassart 36, B-1050 Brussels
1995 All rights of reproduction and communication in any form and by any means reserved in
all countries to CEN and its members.
Ref. No. EN 10212:1995 E

EN 10212:1995

Foreword

Contents

This European Standard was prepared by Technical

Committee ECISS/TC 20, Methods of chemical
analysis, the secretariat of which is held by SIS.
The 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
September 1995, and conflicting national standards
shall be withdrawn at the latest by September 1995.
According with the CEN/CENELEC Internal
Regulations, the following countries are bound to
implement this European Standard: Austria,
Belgium, Denmark, Finland, France, Germany,
Greece, Iceland, Ireland, Italy, Luxembourg,
Netherlands, Norway, Portugal, Spain, Sweden,
Switzerland, United Kingdom.

Page
Foreword
2
1
Scope
3
2
Normative references
3
3
Principle
3
4
Reagents
3
5
Apparatus
3
6
Sampling
4
7
Procedure
4
8
Expression of results
6
9
Test report
6
Annex A (informative) Precision data
7
Figure 1 Arsine evolution and absorption
apparatus
4
Table 1 Calibration solutions
5
Table A.1 Certified reference materials tested 7

BSI 11-1999

EN 10212:1995

1 Scope
This European Standard specifies a
spectrophotometric method for the determination of
arsenic in steel and iron. The method is applicable
to all types of steel and iron with arsenic contents
from 0,001 % to 0,08 % (m/m).

2 Normative references
This European Standard incorporates by dated or
undated references, 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.
EURONORM 18:1979, Selection and preparation of
samples and test pieces for steel and iron and steel
products.

3 Principle
Dissolution of a test portion in a mixture of nitric
and hydrochloric acids followed by evaporation to
dryness and prolonged heating of the dried residue.
Extraction of the residue with acid, reduction of the
arsenic (As V to As III) by addition of potassium
iodide, ascorbic acid and tin (II) chloride.
Conversion of the arsenic to arsenic hydride (arsine)
with zinc.
Absorption of the evolved arsine in a solution of
silver diethyldithiocarbamate and 1-ephedrin in
trichloromethane.
Spectrophotometric measurement of the
reddish-violet coloured colloid at a wavelength
between 500 nm and 520 nm.

4 Reagents
During the analysis, use only reagents of recognized
analytical quality and only distilled water or water
of equivalent purity.
4.1 Iron, of high purity, free of arsenic or of known
low arsenic content.
4.2 Zinc, of high purity, free of arsenic or of known
low arsenic content.
Zinc shot, 0,5 mm to 2 mm, and zinc pellets,
approximately 5 mm in diameter.
4.3 Hydrochloric acid, approximately 1,19 g/ml.
4.4 Sulfuric acid, approximately 1,84 g/ml,
diluted 1 + 1.

BSI 11-1999

4.5 Hydrochloric-nitric acid mixture. Add 65 ml

nitric acid, approximately 1,40 g/ml, to 100 ml
water; add the resulting diluted acid to 60 ml
hydrochloric acid (4.3) and mix.
4.6 Absorption solution. Dissolve 1,25 g of silver
diethyldithiocarbamate (C5H10AgNS2) and 0,825 g
of 1-ephedrin in approximately 400 ml of
trichloromethane (chloroform) in a 500 ml
volumetric flask. Dilute to the mark with
trichloromethane and mix.
After preparation a small residue may develop.
Filter the solution after at least 20 h and store the
solution in an amber coloured bottle. The solution
can be used after the filtration for at least 3 months.
NOTE The peak wavelength of the silver colloid may vary with
the quality of the reagent and should be determined with each
new batch of reagent.

4.7 Ascorbic acid, 100 g/l solution. This solution

shall be freshly prepared each day.
4.8 Potassium iodide, 150 g/l solution. This solution
shall be freshly prepared each day.
4.9 Tin (II) chloride, 400 g/l in hydrochloric acid
solution. Dissolve 20 g of tin (II) chloride in
approximately 40 ml of hydrochloric acid (4.3).
Transfer to a 50 ml volumetric flask, dilute to the
mark with hydrochloric acid (4.3) and mix.
This solution shall be freshly prepared each day.
4.10 Lead acetate wool. Impregnate cotton wool with
lead acetate trihydrate solution, (10 g/l), squeeze
out the excess solution and dry the wool at 105 C
for several hours.
4.11 Arsenic standard solution, corresponding
to 5 4g of arsenic per ml. Dissolve 0,3301 g of
arsenic trioxide, dried at 105 C, in 20 ml sodium
hydroxide solution (8 g/l). Transfer to a 1 000 ml
volumetric flask, dilute to the mark with water and
mix. Transfer 20,0 ml of this solution to a 1 000 ml
volumetric flask, dilute to the mark with water
and mix.

5 Apparatus
Ordinary laboratory equipment and
5.1 A spectrophotometer, suitable for measuring the
absorbance of the solution at a wavelength
of 500 nm to 520 nm (see 4.6), together with cells
of 40 mm and 10 mm optical path length.
5.2 Apparatus for the evolution and absorption of
arsine, as shown in Figure 1.
NOTE Approximate dimensions are shown in the figure.
Important parameters are an adequate depth of immersion and
sufficient free space around the capillary to allow the bubbles to
rise without agglomeration. If these conditions are satisfied,
variations in the apparatus should be permissible.
It is essential that the arsine absorption is complete. This may be
verified initially for a given piece of apparatus by coupling a
second absorption vessel in series with the first.

EN 10212:1995

NOTE

The dimensions given are the approximate values only.

Figure 1 Arsine evolution and absorption apparatus

6 Sampling

7.2 Blank test

Sampling shall be carried out in accordance with

EURONORM 18.

With each analytical run, carry out the calibration

procedure as specified in 7.4. The zero member of
the calibration series provides automatic
compensation for arsenic in the reagents
see 7.4.3 and the note.

7 Procedure
7.1 Test portion
Weigh, to the nearest 0,0001 g, a test portion
of 0,1 g 0,005 g.
NOTE For coarse samples, where the weighing of 0,1 g may be
inconvenient or where a more representative sample is required,
a larger portion may be dissolved in the acid-mixture (4.5). After
the prolonged heating period and the extraction of the residue in
hydrochloric acid (4.3), an aliquot equivalent to 0,1 g shall be
taken and treated with 10 ml of sulfuric acid (4.4) as specified
in 7.3.1.

BSI 11-1999

EN 10212:1995

7.3 Determination
7.3.1 Preparation of the test solution
Transfer the test portion (7.1) to a 100 ml conical
beaker, add 10 ml of hydrochloric-nitric acid
mixture (4.5), cover the beaker with a watch-glass
and digest until solvent action ceases. Rinse and
remove the watch-glass and heat carefully until all
liquid has been evaporated. Continue to heat the
dried residue at a temperature of 300 C to 350 C
for a period of about 3 h.
Cool, add 10 ml of hydrochloric acid (4.3) and heat
to dissolve the residue.
Add 10 ml of sulfuric acid (4.4) and heat carefully to
remove oxides of nitrogen. Continue heating until
copious white fumes of sulfur trioxide are evolved.
Cool, dilute with water to 40 ml, warming if
necessary to dissolve the precipitated sulfates.
7.3.2 Reduction of arsenic (V) to arsenic (III)
Cool and add in the following order, 5 ml of
potassium iodide solution (4.8), 5 ml of ascorbic acid
solution (4.7) and 3 ml of tin (II) chloride
solution (4.9). Allow to stand for 5 min.
NOTE In the case of an unalloyed steel, the solution, at this
stage should be virtually colourless. Coloration is indicative of
incomplete removal of nitric acid. Optimum conditions for fuming
are best decided in the individual laboratory, with due regard
being taken of the temperature variations occurring across hot
plate surfaces and to spurting if the temperature rises too fast. A
final hot plate temperature of approximately 200 C to 240 C
has been found to be satisfactory.

7.3.3 Evolution of arsine and development of

the colour
Transfer the solution to the evolution flask (5.2),
rinsing with 10 ml to 20 ml of water. Dry the neck of
the flask, add a mixture of 3 g of zinc shot and 3 g of
zinc pellets (4.2) and immediately connect the flask
to the delivery tube by means of the ground glass
stopper. As evolution commences, immerse the
delivery tube into 20 ml of the absorption
solution (4.6) contained in an absorption tube with
a 20,0 ml mark. (See the figure.)
NOTE 1 It is important to avoid crystallization at the tip of the
capillary with the danger of blockage and pressure build-up in
the apparatus. Recommended practice is to lower the delivery
tube slowly into the absorption solution (or conversely, if more
convenient, to raise the absorption vessel) as evolution
commences, so that the inside of the capillary remains dry. At the
end of the experiment, the bore at the tip of the capillary should
be cleaned immediately with a fine wire and rinsed with
trichloromethane to prevent adhesion of dried salts. A multihole
bubbler could be advantageous in minimizing the risk of
blocking, but being more difficult to standardize, may increase
the risk of arsine carry over.
NOTE 2 During the experiment there is inevitably a small
release of trichloromethane vapour. It is recommended that the
apparatus is placed in a fume cupboard or is otherwise
adequately ventilated.

BSI 11-1999

Allow the evolution of arsine to proceed for 30 min.

Remove the absorption tube from the evolution
apparatus and dilute to the 20 ml mark on the tube
with trichloromethane to make up for loss by
evaporation. Mix the solution thoroughly.
7.3.4 Spectrophotometric measurement
Carry out the spectrophotometric measurement at
the peak wavelength (500 nm to 520 nm, see 4.6)
after having set the spectrophotometer (5.1) to zero
absorption in relation to water. Use 40 mm cells for
arsenic contents up to 0,02 % and 10 mm cells for
contents larger than 0,02 %. Control the solution
temperature at the time of measurement to
be 20 C 1 C.
Convert the absorbance readings of the test solution
to micrograms of arsenic by reference to the
appropriate calibration graph (see 7.4).
7.4 Establishment of the calibration graph
NOTE It is essential that the calibration graph is established
for each series of samples.

7.4.1 Preparation of the calibration solutions

Weigh 0,1 g portions of iron (4.1) into a series
of 100 ml beakers. From a burette make additions
of arsenic standard solution (4.11) as shown
in Table 1.
Table 1 Calibration solutions
Arsenic standard
solution (4.11)
ml

0,0
0,5
1,0
2,0
3,0
4,0
8,0
12,0
16,0

Arsenic
added
4g

0
2,5
5
10
15
20
40
60
80

Optical path
length
mm

10 and 40
40
40
40
40
10 and 40
10
10
10

Continue as described in 7.3.1, 7.3.2 and 7.3.3.

7.4.2 Spectrophotometric measurements
Carry out the spectrophotometric measurements
according to the method described in 7.3.4 after
having adjusted the spectrophotometer (5.1) to zero
absorbance in relation to water.
7.4.3 Plotting the calibration graph
Prepare calibration graphs (10 mm and 40 mm
cells) by plotting the absorbance readings against
micrograms of arsenic in the measuring solution.
NOTE Using the calibration graphs as described above results
in an automatic correction of the arsenic in the blank.

EN 10212:1995

8 Expression of results

9 Test report

The arsenic content (As), expressed as a percentage

by mass, is given by the equation:

The test report shall contain the following

particulars:
a) the method of analysis used by reference to this
European Standard;
b) the results obtained;
c) any particular details which may have been
noted during the determination;
d) any operations not specified in this European
Standard or any optional operations which could
have had an influence on the result;
e) all indications necessary for the identification
of the sample;
f) the laboratory and the date of analysis.

m 1 100
m1
As = ------------------------= --------------------6
4
m 10
m 10
where
m is the value of the mass of the test portion
in g
m1 is the value of the mass of arsenic found
in the test solution in 4g

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EN 10212:1995

Annex A (informative)
Precision data

The available data do not permit statistical analysis

according to ISO 5725:1986. The results obtained
show a standard deviation of 0,002 % As at a
concentration level of 0,050 % As.

The method has been tested by analysts of different

laboratories on the certified reference materials
shown in Table A.1.
Table A.1 Certified reference materials tested
Materials

Certified As content %

EURONORM

CRM 077-2
NBS 55e

Unalloyed steel
Open hearth iron

0,007
0,007

EURONORM

CRM 053-1
NBS 82
NBS 4g

High purity iron

Ni-Cr cast iron
Cast iron

0,009
0,009
0,012

BCS 322
CRM 077-1
CRM 039-2
CRM 076-2
BCS 260/3

Unalloyed steel
Unalloyed steel
Unalloyed steel
Unalloyed steel
High purity iron

0,012
0,014
0,018
0,022
0,026

EURONORM

CRM 082-1
BCS 239-3
NBS 6f

Unalloyed steel
Unalloyed steel
Cast iron

0,029
0,032
0,032

EURONORM

CRM 079-1
BCS 453

Unalloyed steel
Unalloyed steel

0,051
0,052

EURONORM
EURONORM
EURONORM

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blank

BS EN 10212:1996

List of references
See national foreword.

BSI 11-1999

BS EN
10212:1996

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