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BRITISH STANDARD

Methods for

Analysis and testing of


coal and coke
Part 106: Ultimate analysis of coal and
coke
Section 106.4 Determination of total
sulfur content
Subsection 106.4.1 Eschka method

BS 1016-106.4.1:
1993

BS 1016-106.4.1:1993

Committees responsible for this


British Standard
The preparation of this British Standard was entrusted by the Solid Mineral
Fuels Standards Policy Committee (SFC/-) to Technical Committee SFC/3,
upon which the following bodies were represented:
British Cement Association
British Coal Corporation
British Gas plc
British Steel Industry
Electricity Industry in United Kingdom
GAMBICA (BEAMA Ltd.)
Power Generation Contractors Association (BEAMA Ltd.)

This British Standard, having


been prepared under the
direction of the Solid Mineral
Fuels Standards Policy
Committee, was published
under the authority of the
Standards Board and comes
into effect on
15 May 1993
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The following BSI references
relate to the work on this
standard:
Committee reference SFC/3
Draft for comment 91/54102 DC
ISBN 0 580 21715 9

Amendments issued since publication


Amd. No.

Date

Comments

BS 1016-106.4.1:1993

Contents
Committees responsible
Foreword
Introduction
1 Scope
2 References
3 Principle
4 Reagents
5 Apparatus
6 Preparation of test sample
7 Procedure
8 Expression of results
9 Precision
10 Test report
Annex A (informative) Derivation of factors used in the
expression of results
Table 1 Test portion for coal
Table A.1 Relative atomic masses
List of references

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Page
Inside front cover
ii
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5
2
5
Inside back cover

BS 1016-106.4.1:1993

Foreword
This Subsection of BS 1016 has been prepared under the direction of the Solid
Mineral Fuels Standards Policy Committee. Part 106 will form a revision of
Part 6 to Part 11 of BS 1016. This Subsection supersedes 8.2 in both
BS 1016-6:1977 and BS 1016-7:1977 which are to be deleted by amendment, from
which the principle changes are as follows.
a) When charging the crucible, some of the 4 g of Eschka mixture is now used
to form a bottom layer in the crucible.
b) A further alternative means, using a Gooch crucible, of filtering the solution
after precipitation of the barium sulfate has been added.
Part 106 is a further Part numbered under a scheme for rationalizing and
restructuring BS 1016. The new series, when complete, will begin with Part 100,
which will include a general introduction. The current Parts are as follows, with
the new Part numbers (which will be given to revisions when they are published)
in parentheses.
Part 1: Total moisture of coal (Part 101);
Part 2: Total moisture of coke (Part 102);
Part 6: Ultimate analysis of coal (Part 106);
Part 7: Ultimate analysis of coke (Part 106);
Part 8: Chlorine in coal and coke (Part 106);
Part 9: Phosphorus in coal and coke (Part 106);
Part 10: Arsenic in coal and coke (Part 106);
Part 11: Forms of sulphur in coal (Part 106);
Part 14: Analysis of coal ash and coke ash (Part 114);
Part 15: Fusibility of coal ash and coke ash (Part 113);
Part 16: Methods of reporting results (Part 100);
Part 17: Size analysis of coal (Part 109);
Part 18: Size analysis of coke (Part 110);
Part 20: Determination of Hardgrove grindability index of hard coal
(Part 112);
Part 21: Determination of moisture-holding capacity of hard coal (Part 103).
The following Parts in the new series have been published.
Part 104: Proximate analysis;
Part 105: Determination of gross calorific value;
Part 107: Caking and swelling properties of coal;
Part 108: Tests special to coke;
Part 111: Determination of abrasion index of coal.
Part 106 will be divided into a number of Sections and Subsections, including the
following.
Section 106.1: Determination of carbon and hydrogen content;
Section 106.2: Determination of nitrogen content;
Section 106.3: Determination of oxygen content;
Section 106.4: Determination of total sulfur content;
Subsection 106.4.1: Eschka method;
Subsection 106.4.2: High temperature combustion method;
Section 106.5: Determination of forms of sulfur;
Section 106.6: Determination of chlorine content;
Subsection 106.6.1: Eschka method;
Subsection 106.6.2: High temperature combustion method;

ii

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BS 1016-106.4.1:1993

Section 106.7: Determination of carbon dioxide content;


Section 106.8: Determination of phosphorus content;
Section 106.9: Determination of arsenic content.
This Subsection is based on ISO 334:1992, published by the International
Organization for Standardization (ISO). It is technically equivalent except for the
following changes.
a) References to the application of the method to brown coals and lignites have
been removed from the main text.
NOTE The method as described for hard coal may also be applied to brown coals and lignites but
in such cases the test sample (see clause 6) should be prepared in accordance with
ISO 5069-2 and, if required, its moisture content should be determined in accordance with
ISO 1015 or ISO 5068.

b) References to British Standards, which are not exactly technically


equivalent to the international standards referred to in ISO 334, have been
substituted.
WARNING. This British Standard does not necessarily detail all the precautions
necessary to comply with the requirements of the Health and Safety at Work
etc. Act 1974 [1] or the Control of Substances Hazardous to Health
Regulations 1988 [2]. Attention should be paid to any appropriate precautions
and the method should be operated only by trained personnel.
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 to iv,
pages 1 to 6, 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.
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iii

iv

blank

BS 1016-106.4.1:1993

Introduction
An alternative reference method to that specified in
this Subsection of BS 1016 is given in 8.3 of
BS 1016-6:1977 and 8.3 of BS 1016-7:1977.
Instrumental methods for a more rapid
determination of total sulfur are now available. If
such a method is to be used, it is important to
demonstrate that the method is free from bias, when
compared to this reference method, and will give
levels of repeatability and reproducibility which are
the same as, or better than, those quoted for the
reference method (see clause 9).

1 Scope
This Subsection of BS 1016 specifies a reference
method for determining the total sulfur content of
hard coal and coke by the Eschka method.

2 References
2.1 Normative references
This British Standard incorporates, by reference,
provisions from specific editions of other
publications. These normative references are cited
at the appropriate points in the text and the
publications are listed on the inside back cover.
Subsequent amendments to, or revisions of, any of
these publications apply to this British Standard
only when incorporated in it by updating or revision.
2.2 Informative references
This British Standard refers to other publications
that provide information or guidance. Editions of
these publications current at the time of issue of this
standard are listed on the inside back cover, but
reference should be made to the latest editions.

3 Principle
A test portion is ignited in intimate contact with
Eschka mixture in an oxidizing atmosphere, to
remove combustible matter and to convert the
sulfur to sulfate. This is then extracted with
hydrochloric acid solution and determined
gravimetrically by precipitation with barium
chloride.

4 Reagents
WARNING. Care should be exercised when
handling the reagents, many of which are
toxic and corrosive.
NOTE During the analysis, unless otherwise stated, use only
reagents of recognized analytical grade and only distilled water
or water of equivalent purity.

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4.1 Eschka mixture. Mix two parts by mass of light,


calcined magnesium oxide with one part by mass of
anhydrous sodium (or potassium) carbonate. The
mixture shall entirely pass a test sieve of 212 4m
nominal size of openings.
4.2 Hydrochloric acid, concentrated,
approximately 1.18 g/ml,
approximately 36 % (m/m).
4.3 Potassium sulfate, solution. Weigh, to the
nearest 0.1 mg, about 2 g of potassium sulfate,
previously dried at a temperature of 105 C
to 110 C. Dissolve in water and dilute to 1 l.
4.4 Barium chloride, approximately 85 g/l solution.
Dissolve 100 g of barium chloride dihydrate in water
and dilute to 1 l. Filter before use through a
close-textured, doubly acid-washed filter-paper of
filter-paper pad.
4.5 Methyl red, indicator solution. Dissolve 1 g
of 2-(4-dimethylaminophenylazo)benzoic acid,
sodium salt (methyl red) in 1 l of water.
4.6 Ammonia, concentrated solution, not less
than 25 % (m/m).
4.7 Silver nitrate, 17 g/l solution. Dissolve 17 g of
silver nitrate in water and dilute to 1 l. Store in a
dark glass bottle.

5 Apparatus
5.1 Analytical balance, capable of weighing to the
nearest 0.1 mg.
5.2 Graduated glassware, conforming to the
requirements for class A in the appropriate British
Standards.
5.3 Electrically heated muffle furnace, capable of
being maintained at a temperature
of 800 C 25 C. The ventilation through the
muffle furnace shall be such as to give about 5 air
changes per minute.
5.4 Crucible, of platinum, silica or glazed porcelain,
of capacity approximately 25 ml.
5.5 Flat plate, 6 mm thick, of silica (or other suitable
refractory material), which fits easily into the
muffle furnace (5.3).
5.6 Gooch crucible, of glazed porcelain or sintered
glass.
5.7 Air oven, capable of being maintained at a
temperature of 130 C 10 C.

6 Preparation of test sample


The test sample is the general analysis test sample
prepared in accordance with BS 1017-1:1989 or
BS 1017-2:1960, as appropriate. Expose the sample,
in a thin layer, for the minimim time required for
the moisture content to reach approximate
equilibrium with the laboratory atmosphere.
1

BS 1016-106.4.1:1993

Before commencing the determination, thoroughly


mix the test sample for at least 1 min, preferably by
mechanical means.
If the results are to be calculated other than on an
air-dried basis (see clause 8), then, after weighing
the test portion (see 7.1), determine the moisture
content using a further portion of the test sample by
the method described in BS 1016-104.1:1991 or
BS 1016-104.2:1991, as appropriate.

NOTE The cracking of porcelain crucibles can be prevented, if


they are slowly cooled by insertion in supports of light porous
firebrick on removal from the muffle furnace.

7 Procedure

7.4 Recovering the residue

7.1 Test portion

Transfer the ignited mixture from the crucible to


a 400 ml beaker containing 25 ml to 30 ml of water.
If unburnt particles are present, the determination
shall be stopped and the test repeated. Wash the
crucible thoroughly with about 50 ml of hot water,
and add the washings to the contents of the beaker.

7.1.1 For coal


Take a test portion of the mass given in Table 1 (for
the expected total sulfur content), weighing to the
nearest 0.1 mg.
Table 1 Test portion for coal
Expected total sulfur
content

Mass of test portion

% (m/m)

<5
5 to 10
> 10

1.0
0.5
0.25

7.1.2 For coke


Take a test portion of 1 g, weighing to the
nearest 0.1 mg.
7.2 Charging the crucible
Cover the bottom of the crucible (5.4) uniformly
with 0.5 g of the Eschka mixture (4.1), weighed to
the nearest 0.1 mg. Mix the test portion intimately
with 2.5 g of the Eschka mixture, weighed to the
nearest 0.1 mg, in a suitable vessel. Transfer the
mixture to the 25 ml crucible. Level the contents by
tapping the crucible gently on the bench and cover
the contents uniformly with 1.0 g of the Eschka
mixture, weighed to the nearest 0.1 mg.
NOTE The entire 4 g of the Eschka mixture should be weighed
out and the 0.5 g and 1 g portions, required for the bottom and
top layers, should be extracted from this. For this purpose, it is
convenient to calibrate a small glass tube for each batch of
Eschka mixture, to deliver 0.5 g and 1 g without weighing. The
bottom layer of Eschka mixture below the test portion mixture
reduces attack on the porcelain surface, so that the extraction of
sulfate with hot water is complete even when the surface
deteriorates.

7.3.2 For coke


Place the charged crucible (or crucibles) on the cold
insulating plate (5.5) and insert into the muffle
furnace (5.3) at a temperature of 800 C 25 C,
maintaining this temperature for at least a
further 1.5 h. Withdraw the crucible (or crucibles)
and allow to cool (see note to 7.3.1).

7.5 Extraction
Place a watch-glass on the beaker and then, while
tilting the watch-glass, carefully add enough
hydrochloric acid (4.2) to dissolve the solid
matter (17 ml will normally be required), warming
the contents of the beaker to effect solution. Boil
for 5 min to expel carbon dioxide and filter,
collecting the filtrate in a 400 ml conical beaker.
NOTE A medium-textured, doubly acid-washed filter-paper or
a filter-paper pad is recommended for speed of filtration.
To prepare the filter-paper pad, shake doubly acid-washed
filter-paper clippings, in pieces with areas of
approximately 1 cm2, with water in a bottle until the paper is
thoroughly disintegrated. Place a porcelain filter cone of 25 mm
diameter in a 75 mm funnel, close the stem of the funnel with a
finger and add water until the cone is immersed and the funnel
stem is full. Shake, onto the cone, sufficient paper pulp to form a
pad 5 mm thick, and level it with a fiat-ended glass rod. Allow the
excess water to drain away by removing the finger from the stem
and as drainage ceases, lightly tamp the pad round the edges
with the glass rod. A final wash with water renders the filter
ready for use.

Wash the filter with five 20 ml portions of hot water.


Add 2 or 3 drops of the methyl red indicator
solution (4.5) to the combined filtrate and washings,
and then cautiously add the ammonia solution (4.6)
until the colour of the indicator changes and a trace
of precipitate is formed. Add enough hydrochloric
acid (4.2) to just redissolve the precipitate and then
add 1 ml in excess.

7.3 Ignition
7.3.1 For coal
Place the charged crucible (and any others up to the
limit of the muffle furnace capacity) in the cold
muffle furnace (5.3) and raise the temperature
to 800 C 25 C in about 1 h, maintaining this
temperature for at least a further 1.5 h. Withdrawn
the crucible (or crucibles) and allow to cool.

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BS 1016-106.4.1:1993

7.6 Precipitation of barium sulfate

7.7 Blank test

After extraction, dilute the solution, if necessary, to


approximately 200 ml and cover the beaker
containing the solution with a watch-glass. Heat the
covered beaker until the solution boils and then
reduce the heating slightly until ebullition of the
solution ceases. Then add 10 ml of the cold barium
chloride solution (4.4) from a pipette with a delivery
time of approximately 20 s, so that the barium
chloride solution falls into the centre of the hot
solution, while it is being agitated. Keep the solution
just below boiling point for 30 min.
Filter the solution using one of the following
techniques.
a) By gravity through an ashless, close-textured,
doubly acid-washed filter-paper of
diameter 100 mm to 125 mm. Carefully fold the
filter-paper and fit it into a fluted,
long-stemmed 60 funnel, so that the stem
remains full of liquid during the filtration.
b) By gravity through a filter-paper pad prepared
from ashless, doubly acid-washed
filter-paper (see note to 7.5).
c) By suction through a pad of filtration mineral
fibre in a Gooch crucible (5.6). Before
commencing the filtration, dry the Gooch crucible
and pad for 1 h at a temperature
of 130 C 10 C and weigh, to the
nearest 0.1 mg.
Wash the precipitate with hot water, using not more
than 250 ml, until the last 20 ml of the washings
give not more than a faint opalescence with the
silver nitrate solution (4.7).
If technique a) or b) is used, place the wet
filter-paper or pad in the previously ignited and
weighed crucible (5.4) on the cold flat plate (5.5).
If technique b) is used, after transferring the
filter-paper pad to the crucible, wipe the funnel
successively with two halves of an ashless
filter-paper and place this paper in the crucible with
the pad. Insert the crucible slowly into the muffle
furnace (5.3), at a temperature of 800 C 25 C,
and then heat for 15 min. Cool in a desiccator and
reweigh, to the nearest 0.1 mg.
If technique c) is used, dry the Gooch crucible (5.6)
and pad for 1 h at a temperature of 130 C 10 C,
cool in a desiccator and reweigh, to the
nearest 0.1 mg.

Carry out a blank test using the same procedure as


for the determination, but omitting the test portion
(as described in 7.2 to 7.6). Using a one-mark
pipette, add 25.0 ml of the potassium sulfate
solution (4.3) to the filtrate before adding the
methyl red indicator solution (4.5), as described
in 7.5.

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8 Expression of results
The sulfur content, ws, of the sample, expressed as a
percentage by mass, is given by the equation

where
m1
m2
m3
k

2so4

is the mass, expressed in grams, of the


test portion;
is the mass, expressed in grams, of
barium sulfate found in the
determination;
is the mass, expressed in grams, of
barium sulfate found in the blank test;
is the mass concentration expressed in
grams per litre, of the potassium
sulfate solution (4.3).

NOTE The derivation of the factors used in the equation is


given in Annex A.

Report the result, as the mean of duplicate


determinations, to the nearest 0.1 % (m/m).
The results of the determination described in this
standard are reported on the air-dried basis.
Calculation of the results to other bases is dealt with
in BS 1016-16:1981.

9 Precision
9.1 Repeatability limit
The results of duplicate determinations, carried out
at different times, in the same laboratory, by the
same operator with the same apparatus on
representative portions taken from the same test
sample, should not differ by more than 0.05 %
absolute.
9.2 Reproducibility critical difference
The means of the results of duplicate
determinations, carried out in each of two
laboratories on representative portions taken from
the same sample after the last stage of sample
preparation, should not differ by more than 0.1 %
absolute, at a 95 % confidence level.

BS 1016-106.4.1:1993

10 Test report
The test report shall include the following
particulars:
a) the identification of the sample;
b) the method used, i.e. BS 1016-106.4.1:1993;
c) the date of the test;

d) the results expressed in accordance with


clause 8;
e) any unusual features noted during the
determination;
f) any operation not included in this standard or
regarded as optional.

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BS 1016-106.4.1:1993

Annex A (informative)
Derivation of factors used in the expression of results
In this annex, relative atomic masses and relative molecular masses are represented by the chemical
formulae in square brackets. The relative atomic masses given in Table A.1 were used in the calculations.
Table A.1 Relative atomic masses
Element

Symbol

Relative atomic mass

Barium

Ba

137.33

Oxygen

15.999

Potassium

39.098

Sulfur

32.06

The mass, expressed in grams, of barium sulfate equivalent to 25 ml of potassium sulfate solution is given
by the formula

where k

2so 4

is the mass concentration, expressed in grams per litre, of the potassium sulfate solution.

Thus, the sulfur content ws of the sample, expressed as a percentage by mass, is given by the equation

where
m1 is the mass, expressed in grams, of the test portion.;
m2 is the mass, expressed in grams, of barium sulfate found in the determination;
m3 is the mass, expressed in grams, of barium sulfate found in the blank test.
Hence

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BS 1016-106.4.1:1993

List of references (see clause 2)


Normative references
BSI standards publications
BRITISH STANDARDS INSTITUTION, London

BS 1016, Methods for analysis and testing of coal and coke.


BS 1016-16:1981, Methods for reporting results.
BS 1016-104, Proximate analysis.
BS 1016-104.1:1991, Determination of moisture content of the general analysis sample of coal.
BS 1016-104.2:1991, Determination of moisture content of the general analysis sample of coke.
BS 1017, Sampling of coal and coke.
BS 1017-1:1989, Methods for sampling of coal.
BS 1017-2:1960, Methods for sampling of coke.

Informative references
BSI standards publications
BRITISH STANDARDS INSTITUTION, London

BS 1016, Methods for analysis and testing of coal and coke.


BS 1016-6:1977, Ultimate analysis of coal.
BS 1016-7:1977, Ultimate analysis of coke.
ISO standards publications
INTERNATIONAL ORGANIZATION FOR STANDARDIZATION (ISO) , Geneva. (All publications are available from BSI Sales.)

ISO 334:1992, Solid mineral fuels Determination of total sulfur Eschka method1).
ISO 1015:1992, Brown coals and lignites Determination of moisture content Direct volumetric
method1).
ISO 5068:1983, Brown coals and lignites Determination of moisture content Indirect gravimetric
method1).
ISO 5069-2:1983, Brown coals and lignites Principles of sampling Part 2: Sample preparation for
determination of moisture content and for general analysis1).
Other references
[1] GREAT BRITAIN. Health and Safety at Work etc. Act 1974. London: HMSO
[2] GREAT BRITAIN. Control of Substances Hazardous to Health Regulations, 1988. London: HMSO

1) Referred

to in the foreword only.

BSI 06-1999

BS 1016-106.4.1:
1993

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