International Standard (!

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INTERNATIONAL
*dliJ# 5997
ORGANIZATION FOR STANDARDIZATIONW4E~YHAPO~HAR OPTAHMSALWR
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fl0 CTAH~FW3ALW.ORGANiSATlON INTERNATIONALE DE NDRMALISATION

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Chromium ores and concentrates - Determination of
silicon content - Molecular absorption spectrometric
method and gravimetric method
Minerais et concentrtk de chrome - Dosage du silicium - Mkthode par spectrom&rie d’absorption mol&ulaire et me’thode
gravilr@trique

First edition - 1984-11-15

ic UDC 553.32 : 543.21 : 543 : 42 Ref. No. IS0 5997-1994 (E)

8 Descriptors : minerals and ores, chromate minerals, chemical analysis, determination of content, silicon, spectrochemical analysis, gravimetric
7
6 analysis.
8
E
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 Foreword
IS0 (the International Organization for Standardization) is a worldwide federation of
national standards bodies (IS0 member bodies). The work of preparing International
Standards is normally carried out through IS0 technical committees. Every 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, govern-
mental and non-governmental, in liaison with ISO, also take part in the work.

Draft International Standards adopted by the technical committees are circulated to

the member bodies for approval before their acceptance as International Standards by
the IS0 Council. They are approved in accordance with IS0 procedures requiring at
least 75 % approval by the member bodies voting.

International Standard IS0 5997 was prepared by Technical Committee ISO/TC 65,
Manganese and chromium ores.

0 International Organization for Standardization, 1984 0

Printed in Switzerland

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 INTERNATIONAL STANDARD IS0 5997-1984 (E)

Chromium ores and concentrates - Determination of

silicon content - Molecular absorption spectrometric
method and gravimetric method

1 Scope and field of application 3.3 Reagents

This International Standard specifies the following methods for 3.3.1 Fusion mixture.
the determination of the silicon content of chromium ores and
concentrates : Mix 106 g of sodium carbonate anhydrous, 50 g of sodium
tetraborate (previously ignited till foaming ceases) and 0,5 g of
- method A : molecular absorption spectrometric potassium nitrate and thoroughly grind in a corundum or hard
method, applicable to products having silicon contents from steel mortar.
0,05 to 0,5 % (m/m);

- method B : gravimetric method, applicable to pro- 3.3.2 Ammonium molybdate, 50 g/l solution.
ducts having silicon contents from 0,5 to 15 % (m/m).
Keep the solution in a polyethylene container. In case of need,
This International Standard should be read in conjunction with the reagent shall be previously recrystallized. For this transfer
IS0 6629. 250 g of the reagent to a 600 ml beaker and dissolve in 400 ml
of water while heating at 70 to 80 ‘X. Filter the solution
through a close-texture filter paper, add 300 ml of ethanol
[96 % h/m11 while mixing and allow to stand for 1 h until the
2 Reference precipitate coagulates.

IS0 6629, Chromium ores and concentrates - Methods of Filter the precipitate with suction on a medium-texture filter
chemical analysis - General instructions. paper, wash two or three times with ethanol and dry in the air.

3.3.3 Hydrochloric acid, Q I,19 g/ml, diluted 1 + 3.

3 Method A - Spectrometric method for
silicon contents from 0,05 to 0,5 % (m/m) 3.3.4 Mixture of acids.

3.1 Principle Dissolve 5 g of citric acid and 1 g of ascorbic acid in 100 ml of

water.
Decomposition of a test portion by fusing with fusion mixture.
Dissolution of the melt in water. Prepare the mixture fresh.

Adjustment of pH of the solution with hydrochloric acid. Reac- 3.3.5 Silicon, standard solution corresponding to 50 mg of Si
tion of the silica with ammonium molybdate and reduction with per litre.
ascorbic acid in the presence of citric acid.
Weigh 0,107 0 g of silicon dioxide, calcined at 1 000 to
Spectrometric measurement at the wavelength 810 nm or 620 1 100 OC to constant mass, into a platinum crucible, add 2 g of
to 640 nm. fusion mixture (3.3.11, mix with a platinum wire, cover with a
platinum lid and fuse at 1 000 to 1 100 ‘X. Transfer the crucible
3.2 Reactions with the melt to a 1 000 ml beaker. Dissolve the melt in 100 to
150 ml of 10 g/l sodium carbonate solution while heating
The method is based on the interaction of silicic acid with am- gently. Cool the solution, dilute with 10 g/l sodium carbonate
monium molybdate with the formation of a yellow silicomolyb- solution to about 750 ml, transfer to a I 000 ml one-mark
date heteropolyacid which is reduced with ascorbic acid to a volumetric flask, dilute with 10 g/l sodium carbonate solution
blue silicomolybdate complex. to the mark and mix.
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 IS0 5997-1984 (El

Keep the solution in polyethylene containers. Table 1

Pipette 25 ml of this solution to a 500 ml beaker, dilute with Expected silicon

water to 350 to 400 ml, acidify with hydrochloric acid (3.3.3) to Aliquot portion
content
adjust to pH 1,5 to 1,7, using the pH meter (3.4.31, transfer to a
500 ml one-mark volumetric flask, dilute with water to the mark
and mix.
0.25 to
0.05 to 0.5
0.25 I 5
10 I
1 ml of this standard solution contains 0,005 0 mg of Si.
Add 1,5 ml of hydrochloric acid (3.3.3) and 60 to 65 ml of water
to each flask. Add 5 ml of ammonium molybdate solution
(3.3.2) to one of the flasks, mix and allow the solutions to stand
3.4 Apparatus for 10 min.

Ordinary laboratory apparatus and Add 5 ml of mixture of acids (3.3.4) to both flasks, dilute with
water to the mark, mix and allow to stand for 15 min.
3.4.1 Platinum crucible, with platinum lid and platinum
wire.
3.6 Spectrometric measurement

3.4.2 Spectrometer with a radiation selector for Measure the absorbance of each solution using the spec-
continuous variation, or trometer (3.4.2) at 810 nm or the spectrometer (3.4.3) at 620 to
640 nm in 20 to 50 mm cells against the solution to which am-
3.4.3 Spectrometer with a radiation selector for monium molybdate solution has not been added as reference.
discontinuous variation.
3.7 Preparation of calibration graph
3.4.4 pH meter.
Introduce, using a burette, into each of a series of six 106 ml
one-mark volumetric flasks 0,O; 2,0; 4,0; 6,0; 8,0; and IO,0 ml
of the standard silicon solution (3.3.51, corresponding to 0,O;
3.5 Procedure 0,005; 0,010; 0,015; 0,020; and 0,025 mg of Si. Add I,5 ml of
hydrochloric acid (3.3.31, 60 to 65 ml of water, and 5 ml of
ammonium molybdate solution (3.3.21, mix and allow the sol-
3.5.1 Test portion
utions to stand for IO min. Then add 5 ml of mixture of acids
(3.3.41, dilute with water to the mark, mix and allow to stand
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Weigh 0,l g of the test sample.1)

for 15 min.

3.5.2 Blank test Measure the absorbance of each solution as specified in 3.6
using the compensation solution as reference.
Carry out the blank test through all stages of the analysis.
Prepare a calibration graph by plotting the absorbance values
3.5.3 Decomposition of test portion against the nominal silicon content.

Transfer the test portion (3.5.1) into a platinum crucible (3.4.11, 3.8 Expression of results
add 2 g of fusion mixture (3.3.11, mix with a platinum wire
(3.4.11, cover with a platinum lid (3.4.1) and fuse at 1 000 to
3.8.1 Calculation
1 100 ‘-‘C. Cool the crucible containing the melt and transferin-
to a 250 ml fluoroplastic beaker. Dissolve the melt while heating
Convert the absorbance reading for the test solution to silicon
gently in 70 to 80 ml of water (if necessary, filter the solution).
content by means of the calibration graph (3.7) deducting the
Cool the solution, acidify with hydrochloric acid (3.3.3) to ad-
absorbance reading for the blank test.
just to pH I,5 to 1,7, using the pH meter (3.4.41, transfer to a
100 ml one-mark volumetric flask, dilute with water to the mark
The silicon (Si) content, expressed as a percentage by mass, is
and mix.
given by the formula

3.5.4 Preparation of test solution m, x 100

XK
m2 X 1000
Pipette suitable aliquot portions of the solution, the volume of
which will depend upon the expected silicon content of the
sample (see table 1) into two 100 ml one-mark volumetric =LxK
flasks.
m2 X 10

1) Sampling and sample preparation of chromium ores will be the subject of IS0 6153 and IS0 6154, respectively.

2
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 IS0 5997-1994 (E)

where CAUTION - Risk of poisoning by inhalation, swallowing

or contact with the skin. Handle in an efficient fume cup-
ml is the mass, in milligrams, of silicon in the aliquot por- board, away from exposed flames, etc. Avoid inhalation
tion of the test solution, obtained from the calibration of fumes and contact with skin, eyes and clothing.
graph;
4.2.5 Hydrochloric acid, e 1,19 g/ml.
m2 is the mass, in grams, of the test portion correspond-
ing to the aliquot portion of the test solution;
4.2.8 Hydrochloric acid, diluted 1 + 4.
K is the conversion factor for the expression of the silicon
content on the dry basis. 4.2.7 Hydrochloric acid, diluted 1 + 9.

3.8.2 Permissible tolerances on results of duplicate 4.2.8 Hydrochloric acid, diluted 1 + 100.
determinations

Table 2 4.2.9 Hydrofluoric acid, e I,13 g/ml, 49 % (m/m) solution.

Silicon content Permissible tolerance 4.2.10 Nitric acid, e 1,4 g/ml.

% (m/ml % bnlml
0,05 to 0.25 0‘02 4.3 Apparatus
0.25 to 0.50 0.05
Ordinary laboratory apparatus and

4 Method B - Gravimetric method for 4.3.1 Iron or nickel crucible, with a nickel rod.
silicon contents from 0,5 to 15 % (m/m)
4.3.2 Platinum crucible.
4.1 Principle
4.3.3 Muffle furnace, capable of being maintained at 1 008
Decomposition of a test portion, by either method 1, or to 1 loo OC.
method 2.

Method 1 : Decomposition by fusion with sodium peroxide, 4.4 Procedure

followed by treatment with hydrochloric and perchloric acids.
4.4.1 Test portion
Method 2 : Decomposition by treatment with nitric and per-
chloric acids.
Weigh a mass of the test sampletj chosen from table 3 in ac-
cordance with the expected silicon content.
Separation of the silicic acid by fuming with perchloric acid and
filtration. Ignition of the residue and weighing. Treatment of
the ignited residue with hydrofluoric and sulfuric acids, ignition Table 3
and reweighing.
Expected silicon Mass of test
4.2 Reagents content portion
% tmlml 9
4.2.1 Sodium peroxide. 0,5 to 2,5 1,o
2,5 to 15,0 Or5
CAUTION - Wear safety glasses during fusion. Keep
away from humidity. Do not allow to come into contact
with organic materials to avoid possible explosion 4.4.2 Blank test
hazards.
Carry out the blank test through all stages of the analysis.

4.2.2 Sodium carbonate, anhydrous.

4.4.3 Decomposition of test portion

4.2.3 Sulfuric acid, e 184 g/ml, diluted 1 + 1. If the decomposition is to be based on method 1, proceed as
instructed in 4.4.3.1. If the decomposition is to be based on
4.2.4 Perchloric acid, e I,50 g/ml. method 2, proceed as instructed in 4.4.3.2.

1) Sampling and sample preparation of chromium ores will be the subject of IS0 6153 and IS0 6154, respectively.
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 IS0 5997-1994 (El

4.4.3.1 Place the test portion (4.4.1) in an iron or nickel cru- Allow the beaker to cool, add 50 ml of hydrochloric acid
cible (4.3.1) and add 8 to IO g of sodium peroxide (4.2.1). (4.2.61, agitate and heat gently to dissolve the soluble salts.
Add about 50 ml of hot water and stir, collect the precipitate on
Mix the content of the crucible with a nickel rod (4.3.1), cover a close-texture filter paper containing a small amount of ashless
with a layer of sodium peroxide (4.2.1) (I to 2 g) and fuse at 800 paper pulp. Rinse the beaker with hot hydrochloric acid (4.2.8)
to 850 OC, regularly mixing the contents of the crucible by using a rubber-tipped glass rod for removing all adhering par-
swirling. ticles of silicic acid. Wash the residue with hot hydrochloric
acid (4.2.8) until free from iron salts and finally two or three
Cool the crucible, place it into a 500 ml fluoroplastic beaker and times with hot water. Discard the filtrate and washings.
cover it with a polyethylene watch-glass, leach the melt with
150 to 200 ml of water. Wash the watch-glass and the crucible Place the residue with the filter paper in a platinum crucible
with hot water and remove the crucible from the beaker. (4.3.21, dry, ashify the filter paper and ignite at 750 to 800 OC.
Carefully add hydrochloric acid (4.25) to the contents of the Allow the crucible to cool, add 2 to 3 g of sodium carbonate
beaker until iron hydroxides dissolve, transfer the solution to a (4.2.21, mix with a spatula and ignite at 900 to 1 000 ‘X to
600 ml glass beaker, add 60 ml of perchloric acid (4.2.41, mix effect complete fusion.
and heat to white fumes of perchloric acid. Continue heating to
maintain this stage until crystallization of salts begins.
Allow the crucible to cool, then place it in the original beaker.
Cover the beaker with a watch-glass. Add 50 ml of
Cool the solution, pour carefully down the inside wall of the
hydrochloric acid (4.2.61, heat gently to dissolve the melt, rinse
beaker 30 ml of hydrochloric acid (4.2.71, followed by 150 to
the crucible with water and remove it from the beaker.
200 ml of water and heat to dissolve the salts.

Collect the precipitate on a close-texture filter paper containing Add 30 ml of perchloric acid (4.2.41, partially remove the cover
a small amount of ashless paper pulp. Rinse the beaker with hot from the beaker and heat until the dense white fumes of per-
hydrochloric acid (4.2.8) using a rubber-tipped glass rod for chloric acid appear.
removing all adhering particles of silicic acid. Wash the residue
10 to 12 times with hot hydrochloric acid (4.2.8) and then two Cover the beaker completely and continue heating, until the
or three times with hot water. Collect the filtrate and washings atmosphere in the beaker is clear. Maintain this stage until most
in a 600 ml beaker. Preserve the residue on the filter. Add 10 ml of the perchloric acid has evaporated, but avoid evaporation to
of perchloric acid (4.2.4) to the filtrate and evaporate to white dryness.
fumes of perchloric acid. Continue to heat to maintain this
stage until crystallization of salts begins. Cool the solution, add Allow the beaker to cool and add 50 ml of hydrochloric acid
40 to 50 ml of hot water, mix and heat to dissolve the salts. (4.2.6). Agitate and heat gently to dissolve the soluble salts,
Filter the residue and wash the filter as before. then rinse the walls of the beaker and dilute to about 100 ml
with hot water.
Combine the residue thus obtained with the main residue of
silicic acid. Retain the filter papers with residues and continue Filter the solution through a close-texture filter paper contain-
according to 4.4.4. ing a small amount of ashless paper pulp. Rinse the beaker with
hot hydrochloric acid (4.2.8) using a rubber-tipped glass rod for
removing all adhering particles of silicic acid. Wash the residue
4.4.3.2 Place the test portion (4.4.1) in a 250 ml beaker and 10 to 12 times with hot hydrochloric acid (4.2.8). then two or
moisten with 5 ml of water. Add 50 to 70 ml of perchloric acid three times with hot water. Retain the filter paper with residue
(4.2.4) and 5 ml of nitric acid (4.2.10). Cover the beaker with a and continue according to 4.4.4.
watch-glass, heat to white fumes of perchloric acid and con-
tinue heating to oxidize chromium.
NOTE - Evaporation should not be taken completely to dryness
because of the hazard involved in heating perchlorate salts. 4.4.4 Treatment of residue

Remove the watch-glass and carefully add hydrochloric acid Place the residue (4.4.3) with the filter paper in a platinum
(4.2.51, drop by drop, along the walls of the beaker until brown crucible, dry, ashify the paper and ignite in the muffle furnace
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fumes of chromyl chloride cease to evolve, chromium being (4.3.1) at 1 000 to 1 100 OC to constant mass.
reduced to the trivalent state. Replace the watch-glass on the
beaker and continue to heat the solution to oxidize chromium
Allow to cool in a desiccator and weigh.
completely. Repeat the distillation of chromyl chloride until the
test portion is completely decomposed. Replace the watch-
Moisten the residue with a few drops of sulfuric acid (4.2.31,
glass on the beaker and continue to heat until the atmosphere
add 3 to 5 ml of hydrofluoric acid solution (4.2.9).
in the beaker is clear. Maintain this stage until most of the
perchloric acid has evaporated, but avoid evaporation to
dryness. Heat gently to remove silicic acid and sulfuric acid. Finally, ig-
nite the crucible for 15 min in the muffle furnace at 1 000 to
CAUTION - While working with chromyl chloride avoid 1 100 oc.
poisoning by inhalation, swallowing or contact with the
skin. Handle in an efficient fume cupboard, away from Allow to cool in a desiccator and weigh. Repeat the treatment
exposed flames, etc. Avoid inhalation of fumes and con- with sulfuric and hydrofluoric acids until constant mass is
tact with skin, eyes and clothing. obtained.

4
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 ISO5997-1994(E)

4.5 Expression of results m’1 is the mass, in grams, of the platinum crucible con-
taining crude silica in the blank test;
4.5.1 Calculation
rn'* is the mass, in grams, of the platinum crucible con-
The silicon (53) content, expressed as a percentage by mass, is taining the impurities in the blank test;
given by the formula
K is the convertion factor for expression of the silicon con-
tent on the dry basis.
[(ml - m2) - (m', - mf2)l
x0,4674x 1OOxK
m0 4.5.2 Permissible tolerances on results of duplicate
determinations
UrnI - m21 - (rn', - m’2H
= x 46,74 x K
m0 Table 4
where
Silicon content Permissible tolerance
m. is the mass, in grams, of the test portion; % b?llm) % b?llm)
0,5 to l,o fJB
ml is the mass, in grams, of the platinum crucible contain-
1.0 to 2,0 0,lO
ing crude silica;
2,0 to 4,0 0,15
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4,0 to 8,0 0,20

m2 is the mass, in grams, of the platinum crucible contain-
8,0 to 15,0 0,25
ing the impurities;

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