Designation: D 2361 02

Standard Test Method for

Chlorine in Coal1
This standard is issued under the fixed designation D 2361; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.

4.1.1 A weighed specimen is burned in a combustion bomb

containing oxygen under pressure and a small amount of
ammonium carbonate solution.
4.1.2 A weighed specimen is mixed with Eschka mixture
and heated at a specified temperature in an oxidizing atmosphere.
4.2 The chlorides contained in the ammonium carbonate
solution noted in 4.1.1 or extracted from the incinerated Eschka
mixture noted in 4.1.2 are determined by potentiometric
titration.

1. Scope
1.1 This test method pertains to the determination of total
chlorine content in a coal sample.
1.2 The values stated in SI units are regarded as the
standard. The values shown in parentheses are for information
only.
1.3 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific hazard
statements, see Note 2 and Section 8.

5. Significance and Use

5.1 The purpose of this test method is to measure the total
chlorine content of coal. The chlorine content of coals may be
useful in the evaluation of slagging problems, corrosion in
engineering processes, and in the total analysis of coal and
coke. When coal specimens are combusted in accordance with
this test method, the chlorine is quantitatively retained and is
representative of the total chlorine content of the whole coal.

2. Referenced Documents
2.1 ASTM Standards:
D 121 Terminology of Coal and Coke2
D 1193 Specification for Reagent Water3
D 2013 Test Method of Preparing Coal Samples for Analysis2
D 3180 Practice for Calculating Coal and Coke Analyses
from As- Determined to Different Bases2
E 144 Practice for Safe Use of Oxygen Combustion
Bombs4
E 832 Specification for Laboratory Filter Paper4

6. Apparatus
6.1 Balance, analytical, with a sensitivity of 0.1 mg.
6.2 Apparatus for Bomb Combustion of the Specimen:
6.2.1 Combustion Bomb, constructed of materials that are
not affected by the combustion process or products. The bomb
shall be designed so that all liquid combustion products can be
completely recovered by washing the inner surfaces. There
shall be no gas leakage during a test. The bomb shall be
capable of withstanding a hydrostatic pressure test of 20 MPa
(300 psig) at room temperature without stressing any part
beyond its elastic limit.
6.2.2 Combustion CrucibleAn open crucible of platinum,
quartz, or acceptable base-metal alloy. Base-metal alloy crucibles are acceptable, if after a few preliminary firings, the
weight does not change significantly between tests.

3. Terminology
3.1 For definitions of terms used in this test method, refer to
Terminology D 121.
4. Summary of Test Method
4.1 The specimen is oxidized by combustion and the contained chlorine is absorbed in alkaline reagents using one of the
following two procedures:

1
This test method is under the jurisdiction of ASTM Committee D05 on Coal
Coke and is the direct responsibility of Subcommittee D05.21 on Methods of
Analysis.
Current edition approved Sept. 10, 2002. Published December 2002. Originally
published as D 2361 65T. Last previous edition D 2361 95 (Reapproved 2001).
2
Annual Book of ASTM Standards, Vol 05.05.
3
Annual Book of ASTM Standards, Vol 11.01.
4
Annual Book of ASTM Standards, Vol 14.02.

NOTE 1Stable crucible weight may be obtained by heat treating

base-metal crucibles in a muffle furnace for 4 h at a temperature of 500C.

6.2.3 Ignition Wire, nickel-chromium (Chromel C) alloy or

iron, 100 mm length, 0.16-mm diameter (No. 34 B&S gage).
Platinum or palladium wire, 0.10-mm diameter (No. 38 B&S
gage), may be used.

Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

D 2361 02
8. Hazards
8.1 PrecautionThe following precautions are recommended for safe operations in the use of the oxygen combustion bomb. Additional precautions are given in Recommended
Practice E 144, for use of oxygen combustion bombs.
8.1.1 The weight of the coal specimen and the pressure of
the oxygen admitted to the bomb must not exceed the bomb
manufacturers recommendation.
8.1.2 Inspect the bomb parts carefully after each use.
Frequently check the threads on the main closure for wear.
Replace the cracked or significantly worn parts. Return the
bomb to the manufacturer occasionally for inspection and
proof testing.
8.1.3 The oxygen supply cylinder should be equipped with
an approved type of safety device, such as reducing valve, in
addition to the needle valve and pressure gage used in
regulating the oxygen feed to the bomb. Valves, gages, and
gaskets shall meet industry safety code.7 Check the pressure
gage periodically for accuracy.
8.1.4 During ignition of a specimen, the operator shall not
permit any portion of his body to extend over the combustion
bomb or its container.
8.1.5 Exercise extreme caution when combustion aids are
employed so as not to exceed the bomb manufacturers
recommendations and to avoid damage to the bomb.
8.1.6 Admit oxygen slowly into the bomb to avoid blowing
powdered material from the crucible.
8.1.7 Do not fire the bomb if it has been filled to greater than
3-MPa (30 atm) pressure with oxygen, if the bomb has been
dropped or turned over after loading, or if there is evidence of
a gas leak when the bomb is submerged in the water bath.

6.2.4 Ignition Circuit, for ignition purposes, capable of

providing 6 to 16-V ac or dc to the ignition wire. The ignition
circuit shall be controlled with a momentary switch to avoid
electrical shock to the operator. An ammeter or pilot light is
required in the circuit to indicate when current is flowing. A
step-down transformer, connected to an ac lighting circuit or
batteries, may be used.
6.2.5 Water BathA container large enough to hold the
combustion bomb with enough cooling water to cover the
bomb and dissipate the heat generated during the combustion
process. The container shall be designed to allow a constant
flow of water around the combustion bomb.
6.3 Apparatus for Eschka Combustion of Specimen:
6.3.1 Crucibles, porcelain, 30-mL capacity, high or lowform, or platinum or silica crucibles of similar size, for igniting
the specimen with the Eschka mixture.
6.3.2 Muffle Furnace, electrically heated, capable of maintaining a uniform hot zone at 675 6 25C, and with good
circulation of air.
6.4 Apparatus for Potentiometric Titration:
6.4.1 Potentiometric Titration Assembly, using silver and
silver-silver chloride electrodes.
7. Reagents
7.1 Purity of ReagentsReagent grade chemicals conforming to the specifications of the Committee on Analytical
Reagents of the American Chemical Society shall be used in all
tests.5
7.2 Purity of WaterUnless otherwise indicated, references
to water shall be understood to mean reagent water conforming
to Type II of Specification D 1193.
NOTE 2Warning: Some reagents used in this test method are hazardous. Follow the precautions listed in the Material Safety Data Sheet of the
manufacturer for each reagent.

9. Sample
9.1 The sample shall be the material pulverized to pass a
250-m (No. 60) sieve in accordance with Method D 2013.

7.3 Ammonium Carbonate SolutionDissolve 10 g of ammonium carbonate ((NH4)2CO3H2O) in 100 mL of water. Use
only a freshly prepared solution.
7.4 Eschka MixtureThoroughly mix two parts by weight
of light calcined magnesium oxide (MgO) with one part of
anhydrous sodium carbonate (Na2CO3).6 The Eschka mixture
shall be as free as possible from chlorides.
7.5 Nitric Acid (1 + 1)Mix equal volumes of concentrated
nitric acid (HNO3, sp gr 1.42) and water.
7.6 OxygenThe oxygen used for combustion shall be free
of combustible matter. Oxygen manufactured from liquid air,
guaranteed to be greater than 99.5 % pure, will meet this
requirement.
7.7 Silver Nitrate, Standard Solution, (0.025 N)Heat
crushed crystalline silver nitrate (AgNO3) at 125C for 2 to 3
h. Dissolve 4.247 g of the dried AgNO3 in water and dilute to
1 L. Store in an amber glass bottle.

10. Procedure
10.1 Procedure for Bomb Combustion Method:
10.1.1 Thoroughly mix the analysis sample of coal. Carefully weigh approximately 1 g 6 0.1 mg into a previously
ignited crucible in which it is to be combusted.
10.1.2 Transfer 5 mL of ammonium carbonate solution into
the combustion bomb. Attach the fuse wire to the bomb
electrodes. Place the crucible with the specimen into the
electrode support of the bomb, and insert the fuse wire so that
it just touches the surface of the specimen.
10.1.3 Assemble the bomb in the normal manner and charge
it with oxygen to a pressure between 2.5 to 3 MPa (25 to 30
atm). Admit oxygen slowly to avoid blowing coal from the
crucible. If the oxygen should exceed the specified pressure, do
not proceed with the combustion. In this case, detach the filling
connection, exhaust the bomb in the usual manner, and discard
the specimen.

5
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
MD.
6
Eschka mixture is also available commercially.

7
Suitable reducing valves and adaptors for 3 to 5-MPa (300 to 500-psi)
discharge pressure are available from commercial sources for compressed gas
equipment.

D 2361 02
conditions, but omitting the coal. Use the same method of
chlorine determination as used in the analysis.
10.4 Potentiometric Titration of the ChlorideTitrate with
0.025 N AgNO3 solution, using silver and silver-silver chloride
electrodes and determine the end point with the potentiometer.

NOTE 3Precaution: See Section 8.

10.1.4 Place the bomb in a cooling water bath with water

flowing around the bomb. Attach the ignition wires from the
firing circuit, and ignite the specimen by pushing the momentary switch on the firing circuit. Allow the bomb to remain in
the cooling water for 15 min to allow cooling and absorption of
soluble vapors within the bomb.
10.1.5 Remove the bomb and release the pressure at a
uniform rate, such that the operation will require not less than
2 min. Examine the bomb interior and discard the test if
unburned or sooty deposits are found.
10.1.6 Thoroughly rinse the bomb, electrodes, and crucible
into a beaker with a fine jet of hot water. Take special care not
to lose any washing water.
10.1.7 Acidify the bomb washings in the beaker with 3 mL
of concentrated HNO3(sp gr 1.42). The clear solution usually
obtained can be used directly for titration. If the ash or ferric
oxide content is high enough to mask the end point of the
titration, filtering is required. Then proceed as directed in 10.4.
10.2 Eschka Method:
10.2.1 Preparation of SpecimenThoroughly mix the
analysis sample in the sample bottle, weigh approximately 1 g
6 0.1 mg of the air-dried coal sample, and mix intimately with
3 g of Eschka mixture in the 30-mL crucible. Cover the coal
mixture in the crucible with a uniform layer of 2 g of Eschka
mixture.
10.2.2 CombustionPlace the crucible in a cold muffle
furnace and gradually raise the temperature to 675 6 25C
within about 1 h. Maintain this maximum temperature for 112
h, then withdraw the crucible. Stir with a platinum or steel wire
and examine to see whether any unburned coal remains. If any
is found, return the crucible to the furnace for an additional 12
h, or until no unburned coal remains.
10.2.3 Preparation of the Chloride SolutionTransfer the
incinerated mixture quantitatively to a beaker. Add a small
quantity of hot water, then cautiously add 40 mL of
HNO3(1 + 1). Cover the beaker with a watchglass, swirling and
stirring the contents occasionally to expedite solution. Filter
the solution through a rapid-filtering, hardened, and acidwashed filter paper conforming to the requirements Class D of
Specification E 832. If a low-ash coal is being tested, it may
not be necessary to filter. To determine the chlorine, proceed as
directed in 10.4.
10.3 Blank DeterminationPrepare a solution for blank
determination containing all the reagents used in the determination, and in the same quantities. If the Eschka method were
used, carry out the blank determination under the same

11. Calculation
11.1 If potentiometric titration (10.4) is used, calculate the
percent chlorine present, D, as follows:
D 5 0.0886~A 2 B!/C

(1)

where:
A = AgNO3 required for titration of the specimen, mL,
B = AgNO3 required for titration of the blank, mL, and
C = specimen weight, g.
12. Precision and Bias
12.1 The precision of this test method for the determination
of Chlorine in coal, are shown in Table 1.
TABLE 1 Concentrations Range and Limits for Repeatability and
Reproducibility for Chlorine in Coal
Repeatability Limit
r

Reproducibility Limit
R

0.03%

0.06%

12.1.1 Repeatability Limit (r)the value below which the

absolute difference between two test results calculated to a dry
basis (Practice D3180) of separate and consecutive test determinations, carried out on the same sample, in the same
laboratory, by the same operator, using the same apparatus on
samples taken at random from a single quantity of homogeneous material, may be expected to occur with a probability of
approximately 95%.
12.1.2 Reproducibility Limit (R)the value below which
the absolute difference between two test results calculated to a
dry basis (Practice D 3180) carried out in different laboratories
using samples taken at random from, a single quanity of
material that is as homogeneous as possible, may be expected
to occur wirh a proability of approximately 95%.
12.2 BiasNo statement regarding the bias of this test
method is made due to the unavailability of a standard coal
sample of known chlorine concentration.
13. Keywords
13.1 chlorine content; coal; coal products; combustion
bomb method

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D 2361 02
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