BRITISH STANDARD BS 1016-106.4.

1:
1993

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

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 Amendments issued since publication
15 May 1993
Amd. No. Date Comments
© BSI 06-1999

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

 BS 1016-106.4.1:1993

Contents

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

© BSI 06-1999 i
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 © BSI 06-1999
 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.

© BSI 06-1999 iii

iv blank
 BS 1016-106.4.1:1993

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

calcined magnesium oxide with one part by mass of
An alternative reference method to that specified in
anhydrous sodium (or potassium) carbonate. The
this Subsection of BS 1016 is given in 8.3 of
mixture shall entirely pass a test sieve of 212 4m
BS 1016-6:1977 and 8.3 of BS 1016-7:1977.
nominal size of openings.
Instrumental methods for a more rapid 4.2 Hydrochloric acid, concentrated, Ô
determination of total sulfur are now available. If approximately 1.18 g/ml,
such a method is to be used, it is important to
approximately 36 % (m/m).
demonstrate that the method is free from bias, when
compared to this reference method, and will give 4.3 Potassium sulfate, solution. Weigh, to the
levels of repeatability and reproducibility which are nearest 0.1 mg, about 2 g of potassium sulfate,
the same as, or better than, those quoted for the previously dried at a temperature of 105 °C
reference method (see clause 9). to 110 °C. Dissolve in water and dilute to 1 l.
4.4 Barium chloride, approximately 85 g/l solution.
1 Scope Dissolve 100 g of barium chloride dihydrate in water
and dilute to 1 l. Filter before use through a
This Subsection of BS 1016 specifies a reference
close-textured, doubly acid-washed filter-paper of
method for determining the total sulfur content of
filter-paper pad.
hard coal and coke by the Eschka method.
4.5 Methyl red, indicator solution. Dissolve 1 g
2 References of 2-(4-dimethylaminophenylazo)benzoic acid,
sodium salt (methyl red) in 1 l of water.
2.1 Normative references
4.6 Ammonia, concentrated solution, not less
This British Standard incorporates, by reference, than 25 % (m/m).
provisions from specific editions of other
publications. These normative references are cited 4.7 Silver nitrate, 17 g/l solution. Dissolve 17 g of
at the appropriate points in the text and the silver nitrate in water and dilute to 1 l. Store in a
publications are listed on the inside back cover. dark glass bottle.
Subsequent amendments to, or revisions of, any of
these publications apply to this British Standard 5 Apparatus
only when incorporated in it by updating or revision. 5.1 Analytical balance, capable of weighing to the
2.2 Informative references nearest 0.1 mg.
This British Standard refers to other publications 5.2 Graduated glassware, conforming to the
that provide information or guidance. Editions of requirements for class A in the appropriate British
these publications current at the time of issue of this Standards.
standard are listed on the inside back cover, but 5.3 Electrically heated muffle furnace, capable of
reference should be made to the latest editions. being maintained at a temperature
of 800 °C ± 25 °C. The ventilation through the
3 Principle muffle furnace shall be such as to give about 5 air
A test portion is ignited in intimate contact with changes per minute.
Eschka mixture in an oxidizing atmosphere, to 5.4 Crucible, of platinum, silica or glazed porcelain,
remove combustible matter and to convert the of capacity approximately 25 ml.
sulfur to sulfate. This is then extracted with 5.5 Flat plate, 6 mm thick, of silica (or other suitable
hydrochloric acid solution and determined refractory material), which fits easily into the
gravimetrically by precipitation with barium muffle furnace (5.3).
chloride. 5.6 Gooch crucible, of glazed porcelain or sintered
glass.
4 Reagents
5.7 Air oven, capable of being maintained at a
WARNING. Care should be exercised when temperature of 130 °C ± 10 °C.
handling the reagents, many of which are
toxic and corrosive. 6 Preparation of test sample
NOTE During the analysis, unless otherwise stated, use only
reagents of recognized analytical grade and only distilled water The test sample is the general analysis test sample
or water of equivalent purity. 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.

© BSI 06-1999 1
BS 1016-106.4.1:1993

Before commencing the determination, thoroughly NOTE The cracking of porcelain crucibles can be prevented, if
mix the test sample for at least 1 min, preferably by they are slowly cooled by insertion in supports of light porous
firebrick on removal from the muffle furnace.
mechanical means.
7.3.2 For coke
If the results are to be calculated other than on an
“air-dried” basis (see clause 8), then, after weighing Place the charged crucible (or crucibles) on the cold
the test portion (see 7.1), determine the moisture insulating plate (5.5) and insert into the muffle
content using a further portion of the test sample by furnace (5.3) at a temperature of 800 °C ± 25 °C,
the method described in BS 1016-104.1:1991 or maintaining this temperature for at least a
BS 1016-104.2:1991, as appropriate. further 1.5 h. Withdraw the crucible (or crucibles)
and allow to cool (see note to 7.3.1).
7 Procedure 7.4 Recovering the residue
7.1 Test portion Transfer the ignited mixture from the crucible to
7.1.1 For coal a 400 ml beaker containing 25 ml to 30 ml of water.
If unburnt particles are present, the determination
Take a test portion of the mass given in Table 1 (for shall be stopped and the test repeated. Wash the
the expected total sulfur content), weighing to the crucible thoroughly with about 50 ml of hot water,
nearest 0.1 mg. and add the washings to the contents of the beaker.
Table 1 — Test portion for coal
7.5 Extraction
Expected total sulfur Mass of test portion
content Place a watch-glass on the beaker and then, while
tilting the watch-glass, carefully add enough
% (m/m) g
hydrochloric acid (4.2) to dissolve the solid
<5 1.0 matter (17 ml will normally be required), warming
5 to 10 0.5 the contents of the beaker to effect solution. Boil
> 10 0.25 for 5 min to expel carbon dioxide and filter,
collecting the filtrate in a 400 ml conical beaker.
7.1.2 For coke NOTE A medium-textured, doubly acid-washed filter-paper or
Take a test portion of 1 g, weighing to the a filter-paper pad is recommended for speed of filtration.
To prepare the filter-paper pad, shake doubly acid-washed
nearest 0.1 mg. filter-paper clippings, in pieces with areas of
7.2 Charging the crucible approximately 1 cm2, with water in a bottle until the paper is
thoroughly disintegrated. Place a porcelain filter cone of 25 mm
Cover the bottom of the crucible (5.4) uniformly diameter in a 75 mm funnel, close the stem of the funnel with a
with 0.5 g of the Eschka mixture (4.1), weighed to 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
the nearest 0.1 mg. Mix the test portion intimately pad 5 mm thick, and level it with a fiat-ended glass rod. Allow the
with 2.5 g of the Eschka mixture, weighed to the excess water to drain away by removing the finger from the stem
nearest 0.1 mg, in a suitable vessel. Transfer the and as drainage ceases, lightly tamp the pad round the edges
mixture to the 25 ml crucible. Level the contents by with the glass rod. A final wash with water renders the filter
ready for use.
tapping the crucible gently on the bench and cover
the contents uniformly with 1.0 g of the Eschka Wash the filter with five 20 ml portions of hot water.
mixture, weighed to the nearest 0.1 mg. Add 2 or 3 drops of the methyl red indicator
NOTE The entire 4 g of the Eschka mixture should be weighed solution (4.5) to the combined filtrate and washings,
out and the 0.5 g and 1 g portions, required for the bottom and and then cautiously add the ammonia solution (4.6)
top layers, should be extracted from this. For this purpose, it is until the colour of the indicator changes and a trace
convenient to calibrate a small glass tube for each batch of
Eschka mixture, to deliver 0.5 g and 1 g without weighing. The
of precipitate is formed. Add enough hydrochloric
bottom layer of Eschka mixture below the test portion mixture acid (4.2) to just redissolve the precipitate and then
reduces attack on the porcelain surface, so that the extraction of add 1 ml in excess.
sulfate with hot water is complete even when the surface
deteriorates.
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.

2 © BSI 06-1999
 BS 1016-106.4.1:1993

7.6 Precipitation of barium sulfate 7.7 Blank test

After extraction, dilute the solution, if necessary, to Carry out a blank test using the same procedure as
approximately 200 ml and cover the beaker for the determination, but omitting the test portion
containing the solution with a watch-glass. Heat the (as described in 7.2 to 7.6). Using a one-mark
covered beaker until the solution boils and then pipette, add 25.0 ml of the potassium sulfate
reduce the heating slightly until ebullition of the solution (4.3) to the filtrate before adding the
solution ceases. Then add 10 ml of the cold barium methyl red indicator solution (4.5), as described
chloride solution (4.4) from a pipette with a delivery in 7.5.
time of approximately 20 s, so that the barium
chloride solution falls into the centre of the hot 8 Expression of results
solution, while it is being agitated. Keep the solution
The sulfur content, ws, of the sample, expressed as a
just below boiling point for 30 min.
percentage by mass, is given by the equation
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 where
filter-paper and fit it into a fluted, m1 is the mass, expressed in grams, of the
long-stemmed 60° funnel, so that the stem test portion;
remains full of liquid during the filtration. m2 is the mass, expressed in grams, of
b) By gravity through a filter-paper pad prepared barium sulfate found in the
from ashless, doubly acid-washed determination;
filter-paper (see note to 7.5). m3 is the mass, expressed in grams, of
c) By suction through a pad of filtration mineral barium sulfate found in the blank test;
fibre in a Gooch crucible (5.6). Before is the mass concentration expressed in
Ôk
commencing the filtration, dry the Gooch crucible 2so4
grams per litre, of the potassium
and pad for 1 h at a temperature sulfate solution (4.3).
of 130 °C ± 10 °C and weigh, to the
NOTE The derivation of the factors used in the equation is
nearest 0.1 mg. given in Annex A.
Wash the precipitate with hot water, using not more Report the result, as the mean of duplicate
than 250 ml, until the last 20 ml of the washings determinations, to the nearest 0.1 % (m/m).
give not more than a faint opalescence with the
The results of the determination described in this
silver nitrate solution (4.7).
standard are reported on the “air-dried” basis.
If technique a) or b) is used, place the wet Calculation of the results to other bases is dealt with
filter-paper or pad in the previously ignited and in BS 1016-16:1981.
weighed crucible (5.4) on the cold flat plate (5.5).
If technique b) is used, after transferring the 9 Precision
filter-paper pad to the crucible, wipe the funnel
9.1 Repeatability limit
successively with two halves of an ashless
filter-paper and place this paper in the crucible with The results of duplicate determinations, carried out
the pad. Insert the crucible slowly into the muffle at different times, in the same laboratory, by the
furnace (5.3), at a temperature of 800 °C ± 25 °C, same operator with the same apparatus on
and then heat for 15 min. Cool in a desiccator and representative portions taken from the same test
reweigh, to the nearest 0.1 mg. sample, should not differ by more than 0.05 %
absolute.
If technique c) is used, dry the Gooch crucible (5.6)
and pad for 1 h at a temperature of 130 °C ± 10 °C, 9.2 Reproducibility critical difference
cool in a desiccator and reweigh, to the The means of the results of duplicate
nearest 0.1 mg. 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.

© BSI 06-1999 3
BS 1016-106.4.1:1993

10 Test report d) the results expressed in accordance with

clause 8;
The test report shall include the following
particulars: e) any unusual features noted during the
determination;
a) the identification of the sample;
f) any operation not included in this standard or
b) the method used, i.e. BS 1016-106.4.1:1993; regarded as optional.
c) the date of the test;

4 © BSI 06-1999
 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 O 15.999
Potassium K 39.098
Sulfur S 32.06

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

where Ô k is the mass concentration, expressed in grams per litre, of the potassium sulfate solution.
2so 4
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

© BSI 06-1999 5
6 blank
 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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