BRITISH STANDARD BS

1016-106.6.1:
1997
ISO 587:1997

Methods for analysis

and testing of coal and
coke —
Part 106: Ultimate analysis of coal and
coke —

Section 106.6 Determination of chlorine

content —

Subsection 106.6.1 Eschka method

ICS 75.160.10
BS 1016-106.6.1:1997

National foreword

This British Standard is the UK implementation of ISO 587:1997. Together

with BS 1016-106.6.2 it will supersede BS 1016-8:1977.
The UK participation in its preparation was entrusted to Technical Committee
SFI/3, Analysis and testing of coal and coke, which has the responsibility to:
— aid enquirers to understand the text;
— present to the responsible international/European committee any
enquiries on the interpretation, or proposals for change, and keep the UK
interests informed;
— monitor related international and European developments and
promulgate them in the UK.
Under a scheme for the rationalizing and restructuring of BS 1016, the parts
numbered from 1 to 21 are being gradually withdrawn and replaced with parts
in a new series. The full list of parts in the new series, together with the
corresponding numbering of the old series and related ISO standards is given
in BS 1016-100 General introduction and sampling report.
A list of organizations represented on this committee can be obtained on
request to its secretary.
Cross-references
The British Standards which implement international or European
publications referred to in this document may be found in the BSI Standards
Catalogue under the section entitled “International Standards Correspondence
Index”, or by using the “Find” facility of the BSI Standards Electronic
Catalogue.
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 ISO title page, pages ii to iv, pages 1 to 5 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.

This British Standard, having

been prepared under the
direction of the Sector Board Amendments issued since publication
for Materials and Chemicals,
was published under the Amd. No. Date Comments
authority of the Standards
Board and comes
into effect on
15 September 1997

© BSI 09-1999

ISBN 0 580 28417 4

 BS 1016-106.6.1:1997

Contents

Page
National foreword Inside front cover
Foreword iii
Text of ISO 587 1

© BSI 09-1999 i
ii blank
BS 1016-106.6.1:1997

Contents
Page
Foreword iii
1 Scope 1
2 Normative references 1
3 Principle 1
4 Reagents 1
5 Apparatus 1
6 Preparation of the test sample 2
7 Procedure 2
8 Expression of results 3
9 Precision 4
10 Test report 4
Annex A (informative) Derivation of factors used in calculations
in this International Standard 5

Descriptors: Fossil fuels, solid fuels, coal, lignite, coke, chemical analysis, determination of content,
chlorine, extraction methods.

ii © BSI 09-1999
 BS 1016-106.6.1:1997

Foreword
ISO (the International Organization for Standardization) is a worldwide
federation of national standards bodies (ISO member bodies). The work of
preparing International Standards is normally carried out through ISO technical
committees. Each 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, governmental and non-governmental,
in liaison with ISO, also take part in the work. ISO collaborates closely with the
International Electrotechnical Commission (IEC) on all matters of
electrotechnical standardization.
Draft International Standards adopted by the technical committees are
circulated to the member bodies for voting. Publication as an International
Standard requires approval by at least 75 % of the member bodies casting a vote.
International Standard ISO 587 was prepared by Technical Committee
ISO/TC 27, Solid mineral fuels, Subcommittee SC 5, Methods of analysis.
This third edition cancels and replaces the second edition (ISO 587:1981), which
has been technically revised.
Annex A of this International Standard is for information only.

© BSI 09-1999 iii

iv blank
 BS 1016-106.6.1:1997

1 Scope 4 Reagents
This International Standard specifies a method of WARNING — Care should be exercised when
determining the chlorine content of hard coal, handling reagents, many of which are toxic
brown coals and lignite, and coke using Eschka and corrosive.
mixture. During analysis, unless otherwise stated, use only
reagents of recognized analytical grade and only
2 Normative references distilled water, or water of equivalent purity.
The following standards contain provisions which, 4.1 For all methods
through reference in this text, constitute provisions
4.1.1 Eschka mixture
of this International Standard. At the time of
publication, the editions indicated were valid. All Mix two parts by mass of light, calcined magnesium
standards are subject to revision, and parties to oxide with one part of anhydrous sodium or
agreements based on this International Standard potassium carbonate. The mixture shall entirely
are encouraged to investigate the possibility of pass a test sieve of 0,212 mm nominal aperture.
applying the most recent editions of the standards 4.1.2 Nitric acid, concentrated, chlorine-free,
indicated below. Members of IEC and ISO maintain approximately 70 % (m/m).
registers of currently valid International Standards.
4.2 For the Volhard and ISE methods
ISO 331:1983, Coal — Determination of moisture in
4.2.1 Silver nitrate, standard volumetric solution,
the analysis sample — Direct gravimetric method.
c(AgNO3) = 0,025 mol/l.
ISO 687:1974, Coke — Determination of moisture in
Heat crushed, crystalline silver nitrate at 125 °C for
the analysis sample.
two to three hours. Dissolve 4,247 g in water and
ISO 1015:1992, Brown coals and lignites — dilute to 1 l. Store in an amber glass bottle.
Determination of moisture content — Direct
volumetric method. 4.3 For the Volhard method only
ISO 1170:1977, Coal and coke — Calculation of 4.3.1 3, 5, 5-trimethylhexan-1-ol.
analyses to different bases. 4.3.2 n-Hexan-1-ol.
ISO 1988:1975, Hard coal — Sampling. 4.3.3 Potassium thiocyanate, standard volumetric
ISO 2309:1980, Coke — Sampling. solution, c(KSCN) . 0,025 mol/l.
ISO 5068:1983, Brown coals and lignites — Dissolve 2,4 g of potassium thiocyanate in water
Determination of moisture content — Indirect and dilute to 1 l. Titrate against the silver nitrate
gravimetric method. solution (4.2.1) and calculate the exact equivalence.
ISO 5069-2:1983, Brown coals and lignites — 4.3.4 Iron(III) alum (ammonium iron(III) sulfate)
Principles of sampling — Part 2: Sample indicator, saturated solution.
preparation for determination of moisture content Saturate 100 ml of water with approximately 125 g
and for general analysis. or iron(III) alum [(NH4)2SO4 · Fe2(SO4)3 · 24H2O]
ISO 9411-1:1994, Solid mineral fuels — Mechanical and add sufficient nitric acid (4.1.2) to remove the
sampling from moving streams — Part 1: Coal. brown colour.
ISO 9411-2:1993, Solid mineral fuels — Mechanical 4.4 For the Mohr method only
sampling from moving streams — Part 2: Coke. 4.4.1 Silver nitrate, standard volumetric solution,
c(AgNO3) = 0,050 mol/l.
3 Principle Weigh 8,494 g of silver nitrate, dried as in (4.2.1),
A known mass of sample is ignited in intimate dissolve in water and dilute to 1 l. Store in an amber
contact with Eschka mixture in an oxidizing glass bottle.
atmosphere to remove combustible matter and to 4.4.2 Potassium chromate, indicator solution.
convert the chlorine to alkaline chlorides. These are
Dissolve 5 g of potassium chromate in 100 ml of
extracted with nitric acid or water and determined
water.
by either the Volhard or the Mohr method, or by
potentiometric titration using an Ion Selective
Electrode (ISE).
5 Apparatus
5.1 Analytical balance, capable of weighing to the
nearest 0,1 mg.

© BSI 09-1999 1
BS 1016-106.6.1:1997

5.2 Graduated glassware, conforming to the NOTE 1 It is convenient to weigh out initially 4 g of the Eschka
requirements for Grade A in the International mixture and to extract the portions required for the bottom and
top layers using a small glass tube, calibrated for each batch of
Standards prepared by ISO/TC 48, Laboratory Eschka mixture, to deliver 0,5 g and 1 g portions without
glassware and related apparatus. weighing. The bottom layer of Eschka mixture reduces attack on
silica and porcelain surfaces so that extraction of chlorine with
5.3 Electrically heated muffle furnace, capable of hot water is complete even when the surface deteriorates.
being maintained at a temperature
For coals, place the charged crucible in the cold
of 675 °C ± 25 °C, with adequate ventilation.
muffle furnace (5.3) and raise the temperature
5.4 Crucible, of platinum, silica or glazed porcelain, to 675 °C ± 25 °C in about one hour. Maintain this
of approximately 25 ml capacity. temperature for a further two hours. Withdraw the
5.5 Flat plate, 6 mm thick, of silica or other suitable crucible and allow to cool.
refractory material, which fits easily into the muffle For coke, place the charged crucible on the cold flat
furnace (5.3). plate (5.5) and insert into the muffle furnace at a
5.6 Potentiometric titration assembly, equipped with temperature of 675 °C ± 25 °C. Maintain this
a chloride ion selective electrode and double temperature for two hours. Withdraw the crucible
junction reference electrode. and allow to cool.
NOTE 2 Cracking of the porcelain crucibles is prevented if they
6 Preparation of the test sample are cooled slowly by insertion into supports constructed from a
light, porous refractory material after removal from the muffle
The test sample is the general analysis test sample furnace.
prepared in accordance with ISO 1988, ISO 2309, 7.2 Completion
ISO 5069-2, ISO 9411-1 or ISO 9411-2 as
appropriate. Ensure that the moisture content of Complete the determination by either the
the sample is in equilibrium with the laboratory Volhard (7.2.1), the Mohr (7.2.2) or the ISE
atmosphere, exposing it, if necessary, in a thin layer method (7.2.3).
for the minimum time required to achieve 7.2.1 Volhard method
equilibrium. Transfer the incinerated mixture to a beaker, wash
Before commencing the determination, thoroughly the crucible with about 125 ml of hot water and add
mix the equilibrated test sample for at least one the washings to the beaker. If unburnt particles are
minute, preferably by mechanical means. present, stop the test and repeat the determination,
If the results are to be calculated other than on an extending the combustion time. Cautiously
“air-dried” basis (see clause 8), then, after weighing add 20 ml of the nitric acid (4.1.2) and cover the
the test portion (see 7.1), determine the moisture beaker with a clock glass, swirling or stirring the
content using a further portion of the test sample by contents, if necessary, to help dissolution.
the method described in ISO 331, ISO 687, If necessary, filter the solution through a
ISO 1015 or ISO 5068, as appropriate. rapid-filtering, hardened, acid-washed filter paper,
collecting the filtrate in a conical flask.1) Wash the
7 Procedure paper with a small quantity of hot water (for
7.1 Combustion example four lots of 5 ml to 10 ml), cool to room
temperature and add 20 ml of the silver nitrate
Weigh, to the nearest 0,1 mg, a test portion of solution (4.2.1) to the flask and mix thoroughly.
approximately 1 g, for samples with an expected Immediately add 5 ml of
chlorine content greater than 0,1 % (m/m), or 2 g for the 3, 5, 5-trimethylhexan-1-ol (4.3.1)
samples with a lower expected chlorine content. or n-hexan-1-ol (4.3.2), shake the solution for one
Cover the bottom of the crucible (5.4) uniformly minute to coagulate the precipitate, add eight to ten
with 0,5 g of the Eschka mixture (4.1.1). Thoroughly drops of the iron(III) alum indicator solution (4.3.4)
mix the test portion with 2,5 g of the Eschka and titrate with the potassium thiocyanate
mixture in a suitable container. Transfer the solution (4.3.3). The end-point is reached when the
mixture to the crucible, level the contents by gently solution becomes faintly orange-pink in colour.
tapping the crucible on the bench and cover
uniformly with a further 1 g of the Eschka mixture.

1) Filtrationis usually unnecessary when using 1 g test portions of low-ash fuels, but is required when dealing with larger test
portions or with high-ash fuels.

2 © BSI 09-1999
 BS 1016-106.6.1:1997

7.2.2 Mohr method where

Transfer the incinerated mixture to a beaker, wash c1 is the concentration, in moles per litre, of the
the crucible with hot water, collect the washings in potassium thiocyanate solution (4.3.3);
the beaker and crush the residue in the beaker with V1 is the volume, in millilitres, of the potassium
a flat-ended glass rod. If unburnt particles are thiocyanate solution (4.3.3) used in the
present, stop the determination and repeat the test
determination (7.2.1);
extending the combustion time.
V2 is the volume, in millilitres, of the potassium
Heat the solution to boiling point and filter, using a
thiocyanate solution (4.3.3) used in the blank
filter paper pad or rapid filtering paper, collecting
test (7.3);
the filtrate in a conical flask. Wash the residue with
five portions (5 ml each) of hot water, collecting the m is the mass, in grams, of the test portion.
washings in the flask. Neutralize the solution with
the nitric acid (4.1.2), using a pH paper. Add ten 8.2 Mohr titration
drops of the potassium chromate indicator (4.4.2) The chlorine content (WCl) of the sample, as
and titrate with the silver nitrate solution (4.4.1). analyzed, expressed as a percentage by mass, is
The end-point is indicated by the first appearance of given by the formula
a brown coloration.
7.2.3 ISE method
Transfer the incinerated mixture to a beaker, wash
the crucible with 50 ml to 70 ml of hot water and
add the washings to the beaker. If unburnt particles where
are present, stop the determination and repeat the c2 is the concentration, in moles per litre, of the
test extending the combustion time. Cautiously silver nitrate solution (4.4.1);
add 20 ml of the nitric acid (4.1.2) and cover the
beaker with a clock glass, swirling or stirring the V3 is the volume, in millilitres, of the silver
contents, if necessary, to help dissolution. nitrate solution (4.4.1) used in the
determination (7.2.2);
If necessary, filter the solution through a
rapid-filtering, hardened, acid-washed filter paper, V4 is the volume, in millilitres, of the silver
collecting the filtrate in a conical flask.2) Wash the nitrate solution (4.4.1) used in the blank
paper with a small quantity of hot water (the total test (7.3);
volume of the filtrate should not exceed 100 ml) and m is the mass, in grams, of the test portion.
cool to room temperature.
Titrate with 0,025 M silver nitrate solution (4.2.1), 8.3 ISE method
using the potentiometric titration assembly (5.6). The chlorine content (WCl) of the sample, as
7.3 Blank test analyzed, expressed as a percentage by mass, is
given by the formula
Carry out a blank test, using the same procedure as
described in 7.1 and 7.2 but omitting the test
portion. This assesses both the chlorine in the
reagents and any contamination in the laboratory
atmosphere. This shall not be quantitatively where
significant. c3 is the concentration, in moles per litre, of the
silver nitrate solution (4.2.1);
8 Expression of results
V5 is the volume, in millilitres, of the silver
8.1 Volhard method nitrate solution (4.2.1) used in the
The chlorine content (WCl) of the sample, as determination (7.2.3);
analyzed, expressed as a percentage by mass, is V6 is the volume, in millilitres, of the silver
given by the formula nitrate solution (4.2.1) used in the blank
test (7.3);
m is the mass, in grams, of the test portion.

2)
Filtration is usually unnecessary when using 1 g test portions of low-ash fuels, but is required when dealing with larger test
portions or with high-ash fuels.

© BSI 09-1999 3
BS 1016-106.6.1:1997

8.4 All methods 9.2 Reproducibility critical difference

Report the results as the mean of duplicate The means of the results of duplicate
determinations, to the nearest 0,01 %. determinations, carried out in each of two
The results of the determination described in this laboratories, on representative portions taken from
International Standard are reported on the the same sample after the last stage of sample
“air-dried” basis. Calculation of results to other separation, should not differ by more than 0,06 %
bases in dealt with in ISO 1170. absolute.

9 Precision 10 Test report

9.1 Repeatability limit The test report shall include the following
information:
The results of duplicate determinations, carried out
at different times within a short interval, in the a) reference to this International Standard;
same laboratory, by the same operator, with the b) an identification of the sample tested;
same apparatus, on representative portions taken c) the results and the method of expression used;
from the same analysis sample, should not differ by
d) any unusual features noted during the
more than 0,03 % absolute.
determination;
e) any operation not included in this
International Standard, or regarded as optional;
f) the date of the test.

4 © BSI 09-1999
 BS 1016-106.6.1:1997

Annex A (informative) A.3 Mohr method

Derivation of factors used in The percentage by mass, WCl, of chlorine in the
calculations in this International sample is given by the formula
Standard
A.1 General
In this annex, relative atomic masses and relative
molecular masses are represented by the chemical
formulae in square brackets.
The following equivalences occur in the where
determinations in this International Standard
c2 is the concentration, in moles per litre, of
[AgNO3] N [Cl]
the silver nitrate solution (4.4.1);
[AgNO3] N [KSCN] V3 is the volume, in millilitres, of the silver
A.2 Volhard method nitrate solution (4.4.1) used in the
The percentage by mass, WCl, of chlorine in the determination (7.2.2);
sample is given by the formula V4 is the volume, in millilitres, of the silver
nitrate solution (4.4.1) used in the blank
test (7.3);
m is the mass, in grams, of the test portion;
35,45 is the relative atomic mass of chlorine, [Cl].

A.4 ISE method

where The percentage by mass, WCl, of chlorine in the
V is the volume, in millilitres, of the silver sample is given by the formula
nitrate solution (4.2.1) used in the
determination (7.2.1) and the blank
test (7.3);
V1 is the volume, in millilitres, of the
potassium thiocyanate solution (4.3.3)
used in the determination (7.2.1);
V2 is the volume, in millilitres, of the where
potassium thiocyanate solution (4.3.3) c3 is the concentration, in moles per litre, of
used in the blank test (7.3); the silver nitrate solution (4.2.1);
c is the concentration, in moles per litre, of V5 is the volume, in millilitres, of the silver
the silver nitrate solution (4.2.1); nitrate solution (4.2.1) used in the
c1 is the concentration, in moles per litre, of determination (7.2.3);
the potassium thiocyanate solution (4.3.3); V6 is the volume, in millilitres, of the silver
m is the mass, in grams, of the test portion; nitrate solution (4.2.1) used in the blank
test (7.3);
35,45 is the relative atomic mass of
chlorine, [Cl]. m is the mass, in grams, of the test portion;
35,45 is the relative atomic mass of
chlorine, [Cl].

© BSI 09-1999 5
BS
1016-106.6.1:
1997 BSI — British Standards Institution
ISO 587:1997
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