543.257.1: 546.

76
U.D.C.:
543.41: 546.76 December 1980

Chemical analysis of ferrous materials

EURONORM
Determination of chromium in steels and irons
Method by Potentiometrie and visual titration 99-80

CONTENTS

1 SCOPE AND HELD OF APPLICATION 7 PROCEDURE

- 7.1 Test portion
2 REFERENCE 7.2 Preparation of the test solution
7.3 Oxidation of the chromium and preparation
3 PRINCIPLE for titration
7.4 Titration
4 REAGENTS
8 EX PRESSION OF RESULTS
8.1 Potentiometrie titration
5 APPARATUS
8.2 Visual titration
6 SAMPLING 9 TEST REPORT

1 SCOPE AND FIELD OF APPLICATION

This EURONORM specifies a method for the determina The method is applicable to chromium contents above
tion of chromium in steel and iron by Potentiometrie or 0.25%. If vanadium is present, titration shall be carried
visual titration. out according to the method set out in 7.4.1.2.

2 REFERENCE

EURONORM 18 Selection and preparation of samples and test pieces for steel and iron and steel products.

3 PRINCIPLE

Dissolution of a test portion with appropriate acids.
Oxidation of the chromium in an acid medium to Cr (VI)
by ammonium peroxydisulphate in the presence of silver
sulphate. T he heptavalent manganese formed is reduced
by the CI' ions.
Reduction of the Cr(VI) by means of a titrated solution of
Fe (II).
The volume of the titration solution of ferrous ammonium
sulphate necessary to reduce the Cr (VI) is determined
directly by observation of the variation in potential to
ascertain the equivalent point or by measuring the excess
of titrated solution of ferrous ammonium sulphate by
means of a titrated solution of Mn (VII) which also serves
as an indicator.

Only the last edition of the EURO NO RMS quoted Is valid

Copyright by the Standardization O ffices of the European Communities' Member States

Page '2

4 REAGENTS

Only reagents of recognized analytical quality shall be 4.11

used throughout the analysis.
Sulphuric acid 1,84 g/ml approximately, diluted 1 + 19
(VA') (1 M approximately).
4.0
Distilled water or water of equivalent purity, which is free
from reducing or oxidizing activity shall be used for the
4.12
preparation of the reagent solutions. Silver sulphate, 5 g/1 solution.

4.1
4.13
Crystallized sodium oxalate (COONa) 2 .
Ammonium peroxydisulphate [(NH4) 2 S 2 0 8 ], 500 g/1 solu
tion.
4.2
Prepare this solution at time of use.
Perchloric acid 1,67 g/ml approximately (12 M approx
imately).
4.14
4.3 Manganese sulphate solution of 4 g/1 of M n S 0 4 - H 2 0
Urea
4.15
4.4
Potassium permanganate, 5 g/1 solution.
Hydrofluoric acid 1,15 g/ml approximately (20 M
approximately).
4.16
4.5 Sodium nitrite, 3 g/1 solution.

Orthophosphoric acid 1,70 g/ml approximately (15 M

approximately). 4.17
Sulphamic acid (NH 2 S0 3 H), 100 g/1 solution.
4.6
This solution remains stable for one week only.
Nitric acid 1,40 g/ml approximately (14 M approxi
mately).
4.18
4.7 Potassium dichromate, 0.1 reference solution.

Hydrochloric acid 1,19 g/ml approximately, diluted 1 + Preparation of the solution:

1 (V/V) (6 M approximately). Weigh, to the nearest 0.001 g, 4.903 g of potassium di
chromate previously dried at 150C until a constant
cooled mass is obtained in the dessiccator.
4.8
Using non-reducing water (4.0) transfer the weighed and
Hydrochloric acid 1,19 g/ml approximately, diluted previously dissolved mass quantitatively into a 1 000 ml
1 + 10 (V/V) (1 M approximately). volumetric flask, make up the volume and mix.
1 ml of this reference solution contains 1.733 mg of Cr
4.9 (VI).

Sulphuric acid 1,84 g/ml approximately, diluted 1 + 1

(V/V) (9 M approximately). 4.19
Ferrous ammonium sulphate [Fe(NH 4 ) 2 (S0 4 ) 2 -6H 2 0],
4.10 46 g/1 solution in a M sulphuric medium.

Sulphuric acid 1,84 g/ml approximately, diluted 1 + 5 1 ml of this solution corresponds to approximately 2 mg
(V/V) (3 M approximately). of chromium.

4.19.1 Potentiometrie calibration of the solution
Take 30.0 ml of the potassium dichromate (4.18) refer
ence solution, and transfer it to a 600 ml beaker, add 45
ml of the sulphuric acid solution (4.10) and make up to
approximately 400 ml with water.
Titrate according to the conditions specified in 7.4.1.1.
The corresponding concentration (Ti) of the ferrous
ammonium solution (4.19), expressed in milligrams of
chromium per millilitre, is given by the formula:
V, 1.733
=
where
is the volume in millilitres, of the potassium dichro
mate reference solution (4.18) taken for the calibra
tion (in the present case 30 ml),
V2 is the volume, in millilitres, of the ferrous
ammonium sulphate solution (4.19) used for the
calibration,
1.733 is the mass in milligrams, of Cr (VI) contained in 1
ml of the reference solution (4.18).
4.19.2 Visual calibration of the solution (to be car
ried o u t just before use).
Take 25 ml of the ferrous ammonium sulphate solution
(4.19) and dilute to 325 ml with sulphuric acid (4.11).
Titrate using the potassium permanganate solution (4.20)
until a slight violet colour persists.
To determine the blank, titrate a mixture of 25 ml of
water (4.0) and 325 ml sulphuric acid (4.11) using the
potassium permanganate solution (4.20).
The concentration (Ti) of the ferrous ammonium solution
(4.19) expressed in milligrams of chromium per millilitre,
is given by the formula:
7", = T2 ' '"
25
where
T2 is the concentration of the potassium permanganate
solution (4.20) expressed in milligrams of chromium
per millilitre,
V is the volume in millilitres, of titrated permanganate
solution (4.20) used to oxidize 25 ml of ferrous
ammonium solution (4.19),
V0 is the volume, in millilitres, of titrated potassium per-
manganate solution (4.20) used to titrate the blank
test.
5 APPARATUS
The apparatus consists of ordinary laboratory equipment, and
5.1 Potentiometrie titration device
which permits a difference in potential to be measured
with a saturated platinum-calomel measuring cell.
Page 3
4.20
Potassium permanganate solution, 0.1 N.
4.20.1 Preparation of the solution
Dissolve 3.2 g of potassium permanganate in 1 1 of water
(4.0). After storage in complete darkness for two weeks,
filter on thick fritted glass without washing. Keep the sol-
ution in a coloured glass bottle and avoid contact with
organic matter.
4.20.2 Calibration of the solution
Boil 250 ml of the sulphuric acid solution (4.11) in a 600
ml beaker for 10 min and allow to cool. Weigh, to the
nearest 0.001 g, 0.300 g of sodium oxalate (4.1) previ-
ously dried at 105C and cooled in the dessiccator. Dis-
solve the salt in the boiled sulphuric acid solution (4.11).
Add 39 ml to 40 ml of the potassium permanganate solu-
tion at a rate of 25 ml to 35 ml/min, stirring gently. The
violet colour of the permanganate will disappear in
approximately 45 s. Heat to 70 C to 75 "C and complete
the titration.
Towards the end, titration must be very slow and each
drop should be allowed to become colourless before the
next is added.
To determine the blank, titrate 250 ml of the sulphuric
acid solution (4.11), as described above, concurrently.
The concentration {T2) of chromium in solution, expres-
sed in milligrams per millilitre, is given by the formula:
300 1.733
6.697 (V, V0)
where
V, is the volume in millilitres, of the potassium per-
manganate solution (4.20) used for titrating the
sodium oxalate,
V0 is the volume in millilitres, of the potassium per-
manganate solution (4.20) used for titrating the
blank of the sulphuric acid (4.11),
6.697 is the molecular mass of sodium oxalate divided by
20,
300 is the weighed mass in milligrams of sodium oxalate
(4.1),
1.733 is the mass in milligrams of Cr (VI) contained in 1
ml of the reference solution (4.18).
Page 4
6 SAMPLING
Sampling shall be carried out in accordance with EURONORM 18.
7 PROCEDURE
Warning
Perchloric acid vapours may cause explosions in the
presence of ammonia or organic matter in general.
7.1 Test portion
The masses (m) given below as a function of presumed
chromium content are weighed to the nearest 0.001 g,
remaining within the tolerance of 10% of the specified
mass:
(a) content from 0.25% to 2 % , m approximately 2 g;
(b) content from 2 % to 10%, m approximately 1 g;
(c) content above 10%,m approximately 0.5 g.
7.2 Preparation of the test solution
7.2.1 Unalloyed steels and irons
Place the test portion (7.1) in a 600 ml beaker, add 60 ml
of the sulphuric acid solution (4.10) and 10 ml of the
orthophosphoric acid solution (4.5), and oxidize the solu-
tion with the nitric acid solution (4.6). Heat until large
quantities of white fumes are given off; cool and then add
a further 100 ml of water.
To accelerate the dissolution of a test portion which has a
high silicon content, a few drops of the hydrofluoric acid
solution (4.4) may be added.
7.2.2 Chromium and/or nickel alloy steels
irons 1
Place the test portion (7.1) in a 600 ml beaker, add 25 ml
of the hydrochloric acid solution (4.7) and oxidize with
the nitric acid solution (4.6). If dissolution proves to be
particularly difficult, add 1 ml to 2 ml of the hydrofluoric
acid solution (4.4). Then add 20 ml of the sulphuric acid
solution (4.9) and 10 ml of the orthophosphoric acid solu-
tion (4.5), and heat until dense white fumes are given off.
Add the nitric acid solution (4.6) to the solution while
fumes are still being given off, more than once if neces-
sary, until the carbides have completely dissolved.
7.2.3 Steels containing tungsten
Transfer the test portion (7.1) into a 600 ml beaker, add
25 ml of the hydrochloric acid (4.7) then 20 ml of the
If the silicon concent of the iron exceeds 0.5% proceed as described
in 7.2.4.
sulphuric acid solution (4.9) and 10 ml of the orthophos-
phoric acid solution (4.5) and heat until effervescence has
ceased. If dissolution proves to be particularly difficult
add 1 ml to 2 ml of the hydrofluoric acid solution (4.4).
Oxidize the solution with the nitric acid solution (4.6)
then heat until dense white fumes are given off.
Add the nitric acid solution (4.6) to the solution while
fumes are still being given off, more than once if neces-
sary, until the carbides have completely dissolved.
7.2.4 High alloy steels and irons or steels and irons
with high silicon content
Transfer the test portion (7.1) into a 750 ml Erlenmeyer
flask, add 20 ml of the hydrochloric acid solution (4.7),
10 ml of the nitric acid solution (4.6) and 1 ml of the
hydrofluoric acid solution (4.4).
When effervescence has ceased, add 30 ml of the per-
chloric acid solution (4.2). Heat until white fumes are
given off, cover with a watch glass and continue to heat
until the alloy has completely dissolved (the white fumes
are released from the solution without leaving the flask).
Allow to cool.
Add 30 ml of water, boil for 5 min, allow to cool. Trans-
fer quantitatively into a 600 ml tall form beaker and add
20 ml of the sulphuric acid solution (4.9) and 10 ml of the
orthophosphoric acid solution (4.5).
and
7.3 Oxidation of the chromium and prepara-
tion for titration
If necessary, to remove graphite, filter the test solution
through a cellulose pulp lined filter and wash with the sul-
phuric acid (4.11).
Dilute the solution (7.2) to approximately 350 ml with
warm water (4.0) add 20 ml of the silver sulphate solution
(4.12) and 10 ml of the ammonium peroxydisulphate sol-
ution (4.13).
Cover the beaker with a watch glass and boil the solution
for 10 min. The violet colour of the permanganic acid will
be observed.
If the test portion contains only a very small amount of
manganese, add approximately 5 ml of the manganese sul-
phate solution (4.14) to the solution, so as to render the
formation of the permanganic acid visible. Then, break
down the permanganic acid by adding to the solution,
after it has been brought to the boil, firstly 15 ml of the

hydrochloric acid solution (4.8), then after about 3 min, if
necessary, add a further amount of hydrochloric acid solu
tion, drop by drop, until the violet colour disappears.
Keep the solution on the boil for 10 min until the odour
from the chlorine compounds formed disappears. Cool
rapidly to room temperature.
7.4 Titration
7.4.1 Potentiometrie titration
7.4.1.1 Samples not containing vanadium
Introduce the electrodes of the Potentiometrie device (5.1)
to find the equivalence point in the beaker containing the
solution to be titrated.
Agitate, preferably with an electromagnetic stirrer and
titrate using the titrated ferrous ammonium sulphate solu
tion (4.19) until a potential drop occurs.
Titrate slowly around this point.
With the platinum-calomel measuring cell the potential
drop is of the order of 300 mV and occurs between 700
mV and 900 mV.
Note: With chromium content in solution less than 40 mg
use a 20 ml burette, and with chromium content in
solution more than 40 mg use a 50 ml burette.
7.4.1.2 Samples containing vanadium
Titrate as indicated in 7.4.1.1. In this case the vanadium is
measured along with the chromium. The vanadium
titrated with the chromium is oxidized by means of the
potassium permanganate solution (4.15). To oxidize the
vanadium alone, measure the oxidation potential with the
saturated platinum-calomel measuring cell while the
potassium permanganate solution is being added. Add the
potassium permanganate solution (4.15) drop by drop
until a potential of 1000 mV to 1160 mV is obtained.
8 EXPRESSION OF RESULTS
8.1 Potentiometrie titration
8.1.1 In the absence of v a n a d i u m
The percentage by weight of chromium (Cr) is given by
the expression:
Cr(%) =
v0- 100 =
Vf
m 1000 m 10
Page 5
Maintain this potential for 2 min, after which
either
eliminate the excess potassium permanganate (4.15) by
the addition of approximately 10 ml of the sodium ni
trite solution (4.16). About a minute later add 3 g of
urea (4.3). Wait for the potential to become stabilized
at around 800 mV, agitate and titrate as indicated in
7.4.1.1.
eliminate the excess potassium permanganate (4.15) by
the addition, drop by drop, of the sodium nitrite solu
tion (4.16) until the potential stabilizes at around 770
mV. Add 5 ml of the sulphamic acid solution (4.17)
(potential 780 mV). Then add 30 ml of the orthophos
phoric acid solution (4.5), agitate and titrate as indi
cated in 7.4.1.1.
7.4.2 Visual titration
Reduce the solution prepared in accordance with 7.3 with
the titrated ferrous ammonium sulphate solution (4.19)
which has been measured exactly in a 50 ml burette and is
sufficient to change the solution from an orangish yellow
colour to a greenish blue, add an excess of 5 ml to 10 ml
of this solution. Carry out a back titration immediately
with the titrated potassium permanganate solution (4.20)
until the point of equivalence is reached; the colour of Mn
(VII) shall remain for 1 min.
Note 1: In the absence of vanadium the equivalence point
becomes stable at once. In the presence of van
adium the V (IV) is oxidized slowly by the excess
Mn (VII), which is the reason for the disappear
ance of the violet colour.
Note 2: To begin with it is advisable to titrate slowly;
when the pink colour starts to disappear more
rapidly, the rate of addition can be increased
until the point of equivalence is approached, at
which point the titrated solution (4.20) must
again be added drop by drop.
where
V0 is the volume, in millilitres, of the titrated solution of
ferrous ammonium sulphate (4.19) used for titrating
the chromium,
7~i is the corresponding concentration of the ferrous
ammonium sulphate solution (4.19) expressed in mil
ligrams of chromium per millilitre (4.19.1),
m is the mass, in grams, of the test portion.
Page 6

8.1.2 In the presence of vanadium 8.2 Visual titration

The percentage by weight of chromium (Cr) is given by The percentage by weight of chromium (Cr) is given by
the expression: the expression:
100
(V, V2) , (Vi- V2) , Cr(%) = (V, , V2
Cr(%) = 100 = m 1000
m 1000 m 10
1
where = (V, , V2 T2)
m 10
where
V] is the volume, in millilitres, of the titrated solution of
ferrous ammonium sulphate (4.19) used for titrating Vi is the volume, in millilitres, of the titrated ferrous am
the chromium and the vanadium, monium sulphate solution (4.19) added to reduce the
chromium,
V2 is the volume, in millilitres, of the titrated potassium
V2 is the volume, in millilitres, of the titrated solution of
permanganate solution (4.20) used for the return titra
ferrous ammonium sulphate (4.19) used for titrating
tion,
the vanadium,
7i is the corresponding concentration of the ferrous
ammonium sulphate solution (4.19) expressed in mil
, is the corresponding concentration of the ferrous ligrams of chromium per millilitre (4.19.2),
ammonium sulphate solution (4.19) expressed in mil
T2 is the corresponding concentration of the potassium
ligrams of chromium per millilitre (4.19.1),
permanaganate solution (4.20) expressed in milligrams
of chromium per millilitre (4.20.2),
m is the mass, in grams, of the test portion. m is the mass, in grams, of the test portion.

9 TEST REPORT

The test report shall contain the following particulars:
(a) the method of analysis used by reference to this
EURONORM;
(b) the results obtained, as well as the form in which they
are expressed;
(c) any particular details which may have been noted dur
ing the determination;
(d) any operations not specified in this EURONORM or
any optional operations which could have had an
influence on the result.
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