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Designation: D 6721 – 01

Standard Test Method for

Determination of Chlorine in Coal by Oxidative Hydrolysis
Microcoulometry1
This standard is issued under the fixed designation D 6721; 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.

1. Scope 4. Significance and Use

1.1 This test method covers the determination of total 4.1 This test method permits measurements of the chlorine
chlorine in coal. content of coals.
2. Referenced Documents 5. Interferences
2.1 ASTM Standards: 5.1 Bromides and iodides, if present are calculated as
D 2013 Method of Preparing Coal Samples for Analysis2 chloride. However, fluorides are not detected by this test
D 3173 Test Method for Moisture in the Analysis Sample of method.
Coal and Coke2
D 3180 Practice for Calculating Coal and Coke Analyses 6. Apparatus
from As-Determined to Different Bases2 6.1 Hydrolysis Furnace, which can maintain a minimum
D 4621 Guide for Accountability and Quality Control in the temperature of 900°C.
Coal Analysis Laboratory2 iTeh Standards
D 5142 Test Methods for Proximate Analysis of the Analy-
6.2 Hydrolysis Tube, made of quartz and constructed such
that when the sample is combusted in the presence of tungsten

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sis Samples of Coal and Coke by Instrumental Procedures2
E 29 Practice for Using Significant Digits in Test Data to
accelerator and humidified oxygen, the byproducts of combus-
tion are swept into a humidified hydrolysis zone. The inlet end
Determine Conformance with Specifications3
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shall allow for the introduction and advancement of the sample
2.2 Other Standards boat into the heated zone. The inlet shall have a side arm for the
ISO 5725-6:1994 Accuracy of measurement methods and introduction of the humidified oxygen gas. The hydrolysis tube
results-Part 6: Use in practice of accuracy values4 must be of ample volume, and have a heated zone with quartz
ASTM D6721-01
wool so that complete hydrolysis of the halogens is ensured.
3. Summary of Test Method 6.3 Titration Cell, containing a reference electrode, a work-
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3.1 A 5.00 to 40.00 mg sample of coal is combusted with ing electrode, and a silver sensor electrode, a magnetic stirrer
tungsten accelerator in a humidified oxygen gas flow, at 900°C. as well as an inlet from the hydrolysis tube.
Halogens are oxidized and converted to hydrogenated halides, 6.4 Microcoulometer, capable of measuring the potential of
which are flushed into a titration cell where they accumulate. the sensing-reference electrode pair, comparing this potential
Chlorine is converted to hydrochloric acid. Once the chloride is with a bias potential, and amplifying the difference to the
captured in the electrolyte of the titration cell, it can be working electrode pair to generate current. The microcoulom-
quantitatively determined by microcoulometery, where chlo- eter output voltage should be proportional to the generating
ride ions react with silver ions present in the electrolyte. The current.
silver ion thus consumed is coulometrically replaced and the 6.5 Controller, with connections for the reference, working,
total electrical work needed to replace it is proportional to the and sensor electrodes, for setting operating parameters and for
chloride in the test sample. data integration.
6.6 Hydration Tube, containing water, positioned before the
1
gas inlet on the side arm of the combustion tube, through which
This test method is under the jurisdiction of ASTM Committee D05 on Coal oxygen gas bubbles to provide a hydrated gas flow.
and Coke and is the direct responsibility of Subcommittee D05.29 on Major
Elements in Ash and Trace Elements of Coal. 6.7 Dehydration Tube, positioned at the end of the hydroly-
Current edition approved Oct. 10, 2001. Published November 2001. sis tube so that effluent gases are bubbled through a 95 %
2
Annual Book of ASTM Standards, Vol 05.06. sulfuric acid solution. Water vapor is subsequently trapped
3
Annual Book of ASTM Standards, Vol 14.02.
4
Available from International Organization for Standardization 1 Rue de
while other gases flow into the titration cell.
Varembé, Case Postale 56, CH-1211, Geneva 20, Switzerland

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1
 D 6721 – 01
6.8 Gas-Tight Sampling Syringe, having a 50 µL capacity, 9. Sampling
capable of accurately delivering 10 to 40 µL of standard 9.1 Prepare the analysis sample in accordance with Method
solution. D 2013 to pass a 250-µm (60 mesh) sieve.
6.9 Sample Boats, made of quartz, ceramic or platinum. 9.2 Analyze a separate portion of the analysis sample for
6.10 Balance, analytical, with a sensitivity to 0.00001 g. moisture content in accordance with Test Method D 3173 or
Test Methods D 5142.
7. Reagents and Materials
7.1 Purity of Reagents—Reagent grade chemicals shall be 10. Preparation of Apparatus
used in all tests. Unless otherwise indicated, it is intended that
all reagents shall conform to the specification of the Committee 10.1 Fill the hydration tower with water and connect it to
on Analytical Reagents of the American Chemical Society, the quartz furnace tube inlet.
where such specifications are available. Other grades may be 10.2 Set the furnace temperature to 900°C.
used, provided that the reagent is of sufficiently high purity to 10.3 Adjust the gas flows according to manufacturers speci-
permit its use without lessening the accuracy of the determi- fication, typically 200 mL/min for oxygen and 100 mL/min for
nation. the carrier gas.
7.2 Purity of Water—Unless otherwise indicated, references 10.4 Prepare the sulfuric acid dehydration scrubber, and
to water shall be understood to mean reagent water conforming connect it to the outlet of the quartz furnace combustion tube.
to Specification D 1193, Type II or Type III. 10.5 Clean and prepare the electrode system for the titration
7.3 Acetic Acid (sp gr. 1.05), glacial acetic acid cell per instrument specifications.
(CH3COOH). 10.6 Fill the titration cell with fresh electrolyte solution to
7.4 Argon or Helium, carrier gas, minimum 99.9 % purity. just above the top fill mark.
7.5 Sodium Acetate, anhydrous, (NaCH3CO2), fine granular. 10.7 Place the titration cell on the magnetic stirring device
7.6 Cell Electrolyte Solution—Dissolve 1.35 g sodium ac- and connect the electrode system to the controller. Do not
etate (NaCH3CO2) in 100 mL water. Add to 850 mL of acetic connect the gas flow from the dehydration scrubber to the
titration cell.
iTeh Standards
acid (CH3COOH) and dilute to 1000 mL with water.
7.7 Tungsten Powder, combustion accelerator, (-100 mesh) 10.8 Initiate a conditioning run of the titration cell to
minimum 99.9 % purity. establish titration gain and endpoint values.

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7.8 Oxygen, combustion gas minimum 99.6 % purity.
7.9 Gas Regulators—Use two-stage gas regulators for the the
10.9 Once the titration cell is properly conditioned, connect
gas flow from the dehydration scrubber to the titration cell.
10.10 Let the titration cell stabilize to a background poten-
carrier and combustion gases.
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7.10 Potassium Nitrate (KNO3), fine granular.
7.11 Potassium Chloride (KCl), fine granular.
tial of
10.11
less
To
then 1.0 mv.
ensure quality data, care must be taken to avoid
7.12 Working Electrode Solution (10 % KNO3), Dissolve contaminating the sample boats during the course of the
50 g potassium nitrate (KNO3) in 500 mL of water. ASTM D6721-01 analytical procedure. Do not touch the boats with fingers.
7.13 Inner Chamber Reference Electrode Solution (1 M Handle and transfer the boats using tongs and store said boats
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KCl)—Dissolve 7.46 g potassium chloride (KCl) in 100 mL of in a sealed container such as a glass desiccator, containing no
water. desiccant. Prepare the combustion boats by heating them in the
7.14 Outer Chamber Reference Electrode Solution (1 M combustion tube with oxygen flow for a minimum of five min.
KNO3)—Dissolve 10.1 g potassium nitrate (KNO3) in 100 mL
of water. 11. Recovery Factor
7.15 Sodium Chloride (NaCl), fine granular. 11.1 Confirm the instrument carrier gas and time delay
7.16 Sulfuric Acid (sp gr. 1.84), (H2SO4), concentrated. settings. Typical delays for solvent injections are 2.0 min for
7.17 2,4,6-Trichlorophenol (TCP) (C6H3OCl3), fine granu- carrier gas and 2.5 min to titration start.
lar. 11.2 Inject 10 µL of chlorine standard solution through the
7.18 Methanol (MeOH) (CH3OH), 99.9 % minimum purity. injection port into a prepared combustion boat. Advance the
7.19 Working Chlorine Standard (1µg/µL)—Weigh accu- combustion boat slowly into the heated zone of the furnace.
rately 0.1856 g of 2,4,6-Trichlorophenol to the nearest 0.1 mg. Record the recovered µg Chlorine as RC.
Transfer to a 100 mL volumetric flask. Dilute to the mark with 11.3 Repeat this recovery measurement a minimum of three
methanol. times.
WSCI 5 ~g of TCP 3 0.5386 3 1000/100! (1) 11.4 Calculate the Recover Factor (RF) for each measure-
ment according to Eq 2.
where:
~WSCl 3 10!
TCP = 2,4,6-Trichlorophenol, and RF 5 (2)
RC
WSCI = the working chlorine standard concentration.
where:
8. Hazards RF = the recover factor,
8.1 Consult the current version of OSHA regulations, sup- WSCl = the working chlorine standard concentration, and
plier’s Material Safety Data Sheets, and local regulations for RC = the recovered chlorine value.
all materials used in this test method. 11.5 Calculate the average recovery factor.