Designation: D 4239 – 02a

Standard Test Methods for

Sulfur in the Analysis Sample of Coal and Coke Using High-
Temperature Tube Furnace Combustion Methods1
This standard is issued under the fixed designation D 4239; 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 D 3173 Test Method for Moisture in the Analysis Sample of

1.1 These test methods cover two alternative procedures Coal and Coke2
using high-temperature tube furnace combustion methods for D 3176 Practice for Ultimate Analysis of Coal and Coke2
the rapid determination of sulfur in samples of coal and coke. D 3180 Practice for Calculating Coal and Coke Analyses
1.2 These test methods appear in the following order: from As-Determined to Different Bases2
Sections
D 4208 Test Method for Total Chlorine in Coal by the
Oxygen Bomb Combustion/Ion Selective Electrode
Method A—High-Temperature Combustion Method2
Method with Acid Base Titration Detec-
tion Procedures 6-9
D 4621 Guide for Quality Management in an Organization
Method B—High-Temperature Combustion that Samples or Tests Coal and Coke2
Method with Infrared Absorption Detec- D 5142 Test Methods for the Proximate Analysis of the
tion Procedures 10–12
Analysis Sample of Coal and Coke by Instrumental
NOTE 1—High Temperature Combustion Method with Iodimetric De- Procedures2
tection procedures, formally Method B in the 2000 version of this standard
is still a viable method that may be used. 3. Summary of Test Methods
1.2.1 When automated equipment is used to perform any of 3.1 Method A—High-Temperature Combustion Method with
the two methods of this test method, the procedures can be Acid-Base Titration Detection Procedures—A weighed sample
classified as instrumental methods. There are several manufac- is burned in a tube furnace at a minimum operating temperature
turers that offer to the coal industry equipment with instrumen- of 1350°C in a stream of oxygen. During combustion, all sulfur
tal analysis capabilities for the determination of the sulfur contained in the sample is oxidized to gaseous oxides of sulfur
content of coal and coke samples. (sulfur dioxide, SO2, and sulfur trioxide, SO3) and the chlorine
1.3 This standard does not purport to address all of the in the sample is released as Cl2. These products are then
safety concerns, if any, associated with its use. It is the absorbed into a solution of hydrogen peroxide (H2O2) where
responsibility of the user of this standard to establish appro- they dissolve forming dilute solutions of sulfuric (H2SO4) and
priate safety and health practices and determine the applica- hydrochloric (HCl) acids. The quantities of both acids pro-
bility of regulatory limitations prior to use. See 7.8 and 11.2. duced are directly dependent upon the amounts of sulfur and
chlorine present in the original coal sample. Once the amounts
2. Referenced Documents of each acid present have been determined, the percentage of
2.1 ASTM Standards: sulfur contained in the coal may be calculated.
D 346 Practice for Collection and Preparation of Coke 3.1.1 This method is written to include commercially avail-
Samples for Laboratory Analysis2 able sulfur analyzers that must be calibrated with appropriate
D 1193 Specification for Reagent Water3 certified reference materials to establish recovery factors or a
D 2013 Method of Preparing Coal Samples for Analysis2 calibration curve based on the range of sulfur in the coal or
D 2361 Test Method for Chlorine in Coal2 coke samples being analyzed.
NOTE 2—Elements ordinarily present in coal do not interfere in Method
A (3.1), with the exception of chlorine; results must be corrected for
1
This test method is under the jurisdiction of ASTM Committee D05 on Coal chlorine content of the samples (9.1).
and Coke and is the direct responsibility of Subcommittee D05.21 on Methods of
Analysis. 3.2 Method B—High-Temperature Combustion Method with
Current edition approved Oct. 10, 2002. Published January 2003. Originally Infrared Absorption Detection Procedures—The sample is
approved in 1983. Last previous as D 4239 – 83. Last previous edition approved in
2002 as D 4239 – 02.
burned in a tube furnace at a minimum operating temperature
2
Annual Book of ASTM Standards, Vol 05.06. of 1350°C in a stream of oxygen to oxidize the sulfur. Moisture
3
Annual Book of ASTM Standards, Vol 11.01. and particulates are removed from the gas by traps filled with

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

1
 D 4239 – 02a
anhydrous magnesium perchlorate. The gas stream is passed National Institute of Standards and Technology (NIST) or South African
through a cell in which sulfur dioxide is measured by an Reference Materials (SARMs) from the South African Bureau of Stan-
infrared (IR) absorption detector. Sulfur dioxide absorbs IR dards have proven to be suitable for calibration. Other Certified Reference
Materials can be used provided they are supplied by an internationally
energy at a precise wavelength within the IR spectrum. Energy recognized certifying agency.
is absorbed as the gas passes through the cell body in which the
IR energy is being transmitted: thus, at the detector, less energy METHOD A—HIGH-TEMPERATURE
is received. All other IR energy is eliminated from reaching the COMBUSTION METHOD WITH ACID-BASE
detector by a precise wavelength filter. Thus, the absorption of TITRATION DETECTION PROCEDURES4
IR energy can be attributed only to sulfur dioxide whose
concentration is proportional to the change in energy at the 6. Apparatus
detector. One cell is used as both a reference and a measure- 6.1 Tube Furnace—Capable of heating 150- to 175-mm
ment chamber. Total sulfur as sulfur dioxide is detected on a area (hot zone) of the combustion tube (6.2) to at least 1350°C.
continuous basis. This method is empirical; therefore, the It is usually heated electrically using resistance rods, a resis-
apparatus must be calibrated by the use of certified reference tance wire, or molybdenum disilicide elements. Specific di-
materials. mensions may vary with manufacturer’s design.
3.2.1 This method is for use with commercially available
NOTE 5—Induction furnace techniques may be used provided it can be
sulfur analyzers equipped to carry out the preceding operations
shown that they meet the precision requirements of Section 14.
automatically and must be calibrated using certified reference
materials of known sulfur content based on the range of sulfur 6.2 Combustion Tube—Approximately 28-mm internal di-
in each coal or coke sample analyzed. ameter with a 3-mm wall thickness and 750 mm in length made
of porcelain, zircon, or mullite. It must be gastight at working
4. Significance and Use temperature. The combustion may be carried out in a tapered-
4.1 Determination of sulfur is, by definition, part of the end tube that is closely connected to the gas absorber by
ultimate analysis of coal. high-temperature tubing with gastight joints. Acceptable con-
4.2 Results of the sulfur analysis are used to serve a number figurations include connecting the tapered-end tube directly to
of interests: evaluation of coal preparation, evaluation of the elbow of the fritted gas bubbler or to a 10/30 standard
potential sulfur emissions from coal combustion or conversion taper-ground joint that is attached to a heat-resistant glass right
processes, and evaluation of the coal quality in relation to angle bend. The temperature at the tapered end of the tube
contract specifications, as well as other scientific purposes. should be maintained high enough to prevent condensation in
4.3 The instrumental analysis provides a reliable, rapid the tube itself.
method for determining the concentration of sulfur in a lot of 6.2.1 Alternatively, a high-temperature straight refractory
coal or coke and are especially applicable when results must be tube may be used, if available. It requires a silica adaptor (6.11)
obtained rapidly for the successful completion of industrial, with a flared end that fits inside the combustion tube and serves
beneficiation, trade, or other evaluations. as an exit for the gases.
6.3 Flowmeter, for measuring an oxygen flow rate up to 2.0
5. Sample L/min.
6.4 Sample Combustion Boats, must be made of iron-free
5.1 The sample shall be the material pulverized to pass No.
material and of a convenient size suitable for the dimensions of
60 (250-µm) sieve and mixed thoroughly in accordance with
the instrument being used.
Method D 2013 or Practice D 346.
6.5 Boat Puller—Rod of a heat-resistant material with a
NOTE 3—It may be difficult to meet the precision statements of Section bent or disk end to insert and remove boats from the combus-
14 when high mineral content coals are ground to pass 60 mesh. When the tion tube.
precision of analysis required cannot be obtained, it is recommended that 6.5.1 If the boat puller is to remain within the combustion
the coals be ground to pass through a No. 100 (150-µm) sieve. The
tube while the boat is moved into the hot zone, it is necessary
reduced particle size should result in a more homogeneous sample.
to pass the puller through a T-piece that is fitted into a rubber
5.2 A separate portion of the analysis sample should be stopper at the inlet of the combustion tube. The open end of the
analyzed for moisture content in accordance with Test Method T-piece is sealed with a rubber stopper to permit movement of
D 3173, so that calculation to other than the as-determined the pusher and prevent escape of the oxygen that enters at the
basis can be made. side limb of the T. The rubber stopper or tube should be
5.3 Procedures for converting as-determined sulfur values checked often to avoid leakage.
obtained from the analysis sample to other bases are described 6.6 Gas Absorber or Analyzer Titration Vessel—A narrow
in Practices D 3176 and D 3180. vessel of such diameter that the end of the tube from which the
5.4 Certified Reference Materials, or other commercially
available reference coals or calibrating agents with certified
dry-basis values must be used. The materials must be supplied 4
Based on the method of Mott, R. A., and Wilkinson, H. C., “Determination of
by or have traceability to internationally recognized certifying Sulfur in Coal and Coke by the Sheffield High Temperature Method,” Fuel, Fuel B,
organizations (Note 4). Vol. 35, 1956, p. 6. This method is designed for the rapid determination of sulfur in
coal and coke. It is not applicable to coals or coal density fractions that have been
NOTE 4— Certified Reference Materials such as those available as the subjected to treatment with chlorinated hydrocarbons because of the potentially high
Standard Reference Materials (SRMs) Series 2682 through 2685 from the acidity of the combustion gases.

2
 D 4239 – 02a
gasses exit is inside the vessel and submerged to a depth of at 7. Reagents
least 90 mm, when 200 mL of the peroxide solution (7.4) is 7.1 Purity of Reagents—Reagent grade chemicals shall be
added to the vessel. used in all tests. Unless otherwise indicated, it is intended that
6.6.1 Alternatively, 125-mL capacity bottles with fritted all reagents shall conform to the specifications of the Commit-
disk can be used for gas absorption. The bottles should be of tee on Available Reagents of the American Chemical Society,
such a diameter that the fritted end is covered by the peroxide where such specifications are available.5 Other grades may be
solution to a depth of at least 50 mm. The fritted glass end used, provided it is first ascertained that the reagent is of
porosity should be 15 to 40 µm. The bottles are fitted in a series sufficiently high purity to permit its use without lessening the
of two to the outlet end of the combustion tube. accuracy of the determination.
6.7 Gas-Purifying Train—Designed to be used with specific 7.2 Purity of Water—Unless otherwise indicated, references
instruments, or a U-tube packed with soda asbestos may be to water shall be understood to mean reagent water, Type IV,
used. See configuration in Fig. 1. conforming to Specification D 1193.
6.8 Vacuum Source—Needed if a negative pressure is used 7.3 Aluminum Oxide (Al2O3)—Finely divided and dried at
to transport the gasses and combustion products through the 1350°C.
system. 7.4 Hydrogen Peroxide (H2O2) Solution—One volume per-
6.9 Vacuum Regulating Bottle, containing mercury with an cent (50 mL of 30 % H2O2 with 1450 mL of water). The pH is
open-ended tube dipping into the mercury, used with a vacuum adjusted (using NaOH or H2SO4 as appropriate) to that which
source. is used for the end point in the titration. Solutions should be
6.10 Silica Adaptor, 300 mm long by 8 mm in outside discarded after two or three days.
diameter and flared at one end to 26 mm. To be used with a 7.5 Indicator—Indicators that change color (titration end
straight refractory combustion tube. point) between pH 4 and 5 are recommended, but in no case
6.11 Other Configurations of Apparatus—Complete sulfur should the pH exceed 7. Adequate lighting and stirring to
analyzer assembly units designed to perform functions similar ensure proper detection of the end point is essential. A choice
to this method with automated features that perform the sulfur of indicators or use of a pH meter is permitted (Note 6).
analysis in a more rapid manner are commercially available. Directions for preparing two acceptable mixed indicators are as
These instruments may have combustion tube dimensions and follows:
oxygen-purifying apparatus that differ slightly from those 7.5.1 Mix one part methyl red solution (dissolve 0.125 g in
described in this method, but are acceptable, provided equiva- 60 mL of ethanol and dilute to 100 mL with water) with three
lent values within the precision statement of Section 14 are parts bromcresol green solution (dissolve 0.083 g in 20 mL of
obtained. (See Fig. 2 and Fig. 3.) ethanol and dilute to 100 mL with water). Discard the mixed
solution after one week.

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. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD.

FIG. 1 Apparatus for the Determination of Sulfur Using Acid-Base Titration

3
 D 4239 – 02a

FIG. 2 Apparatus for the Determination of Sulfur by the Iodimetric Detection Method

FIG. 3 Apparatus for the Determination of Sulfur by the Infrared Detection Method

7.5.2 Mix equal volumes of methyl red solution (dissolve 7.8 Oxygen, 99.5 % Pure—Compressed gas contained in a
0.125 g in 60 mL of ethanol and dilute to 100 mL with water) cylinder equipped with a suitable pressure regulator and a
and methylene blue solution (dissolve 0.083 g in 100 mL of needle valve to control gas flow. (Warning—Pure oxygen
ethanol and store in a dark glass bottle). Discard the mixed vigorously accelerates combustion. All regulators, lines, and
solution after one week. valves should be free of grease and oil.)
NOTE 6—Although two end-point indicators or a pH meter method are 8. Procedure
described, the use of the pH meter is accepted as more definitive of the end 8.1 Assemble the apparatus, as directed, by the instructions
point of the titration process and considered to give more reproducible
results.
of the instrument manufacturer. Alternatively, the apparatus
shown in Fig. 1 can be assembled except do not initially
7.6 Soda-Asbestos, 8 to 20 mesh, if a U-tube is used. connect the rubber tube from the oxygen supply to the soda
7.7 Sodium Hydroxide, Standard Solution, 0.05N—Dissolve asbestos U-tube.
2.05 g of sodium hydroxide (NaOH) in water and dilute to 1 L. 8.2 Calibration—Sulfur analyzers must be calibrated at
Standardize against a primary standard. least once on each day they are used, following the analysis

4
 D 4239 – 02a
procedure outlined in Section 8, using coal or coke standards 8.6 Analysis Sample Size—Weigh out 0.5 g of the analysis
(5.4) with sulfur values in the range of the samples being sample to the nearest 0.1 mg for coals containing up to 4.0 %
analyzed. A recovery factor (F) or calibration curve must be sulfur and 0.25 g to the nearest 0.1 mg of analysis sample for
established and appropriately used in each calculation. coals containing over 4.0 % sulfur. Spread the sample evenly in
Actual Sulfur in Standard, Dry Basis a combustion boat.
F 5 Analyzed Sulfur in Standard, Dry Basis (1)
8.6.1 A thin layer of Al2O3 can be used to line the sample
8.3 Furnace Adjustment—Raise the temperature of the fur- boat and cover the sample to ensure complete combustion and
nace to at least 1350°C. Bring the temperature up slowly, reduce splattering or loss of sample.
allowing approximately 3 to 4 h in advance, to allow sufficient 8.7 Sample Combustion—Remove the oxygen baffle or
time to come to a stable temperature. Be sure to check the rubber stopper or both from the combustion tube and put the
manufacturer’s instructions for raising the temperature of the charged sample boat into the inlet end of the combustion tube
furnace and heed any precautions for protecting heating approximately 270 mm from the center of the combustion tube
elements from deterioration or thermal shock. hot zone. Close the combustion tube by replacing the oxygen
8.4 Titration Vessel Preparation—Fill the titration vessel in baffle or rubber stopper or both and, if necessary, readjust the
accordance with the manufacturer’s instructions with approxi- rate of flow of the oxygen. Leave the boat in this position for
mately 200 mL of the gas absorption fluid (hydrogen peroxide) 1 to 3 min until the volatiles have been driven off. This will
(7.4). Adjust the pH of the solution to make it definitely acidic also eliminate the “popping” and soot accumulation in the right
by adding dilute sulfuric acid. If chemical indicators (instead of angle bend. Remove the oxygen baffle or rubber stopper and
a pH meter) are used, add five or six drops of the indicator and move the sample boat slowly forward until the boat is in the
then add a very small quantity (as required) of dilute sodium center of the hot zone, approximately 30 mm at the beginning
hydroxide (NaOH) to reach the end point color that will be of each minute for 6 min is the suggested schedule to ensure a
developed in the sulfur analysis. slow heating rate. Be sure to remove the boat puller from the
hot zone and replace the baffle or stopper after each movement.
8.4.1 If the apparatus with two gas absorption bottles is
Allow the sample to burn in the hot zone for approximately 3
used, add 100 mL of 1 % H2O2(7.4) to the bottles so that at
to 4 min until all sulfur in the sample is oxidized to sulfur
least 50 mm of the fritted disk is covered in the first bottle.
dioxide (SO2) or sulfur trioxide (SO3). The complete sample
8.5 Oxygen Flow—Connect the oxygen supply and adjust burning time is not more than 14 to 15 min. This heating
the oxygen flow to approximately 2 L/min with the oxygen program has been established for all types of coal. Where it is
baffle inserted in the entrance end of the combustion tube. Be shortened for a particular coal or by instruction of the manu-
sure to check manufacturer’s instructions. The flow rate at the facturer of a particular sulfur analyzer, results should be
temperature of 1350°C should be sufficient to prevent the
checked against those obtained by using the longer heating
formation of oxides of nitrogen. Allow the oxygen to flow
schedule.
through the combustion tube for at least 1 min before inserting
any sample. Check the system for any possible leaks. 8.7.1 If the rubber stopper with the T-piece is used (6.5.1),
the rubber stopper remains in the end of the combustion tube
8.5.1 If a vacuum source is used, draw air through the
and the boat puller is permitted movement into the furnace
apparatus at about 350 mL/min, then connect the oxygen
through the T-piece. See Fig. 1.
supply to the U-tube and adjust the rate of flow of the oxygen
to 300 mL/min. The flow rate is adjusted by changing the depth 8.8 Titration—The gasses of combustion leave the combus-
of the penetration into the mercury of the open-ended glass tion tube through the exit end and are dissolved in the hydrogen
tube in the vacuum regulating bottle. The preliminary adjust- peroxide in the gas absorption bottles or analyzer titration
ment to 350 mL/min of air ensures that the connections at the vessel forming a dilute sulfuric acid. Titrate the contents of this
outlet end of the combustion tube are under slightly reduced vessel with 0.05N sodium hydroxide (7.7), backwashing the
internal pressure and no leak of combustion products should titration vessel and inlet tubes according to manufacturer’s
occur. instructions. The total acidity, because of oxides of sulfur and
chlorine, is given according to the following reactions:
NOTE 7—A gastight combustion train must be established with an SO2 + H2O2 → H2SO4
adequate flow of approximately 300 mL/min of pure acid-free oxygen Cl2 + H2O2 → 2HCl + O2
before analyzing samples on the equipment. This is best accomplished
during the period the high-temperature tube furnace is brought to its 8.8.1 If the contents of the gas absorption bottles must be
operating temperature of 1350°C. The required gas flow may be estab- transferred to a suitable titration flask, be sure to wash the
lished by the use of reduced internal pressure, or should the manufacturer bottles and inlet tube or silica adaptor with water (7.2) and add
specify or the operator prefer, it can be obtained by the use of a positive these washings and five or six drops of indicator to the titration
pressure train operated at slightly above atmospheric pressure to obtain the flask before titrating with the 0.05N NaOH solution (7.7).
required oxygen flow rate. In all cases, the instructions of the manufac-
turer of the equipment should be followed. This also applies to the 8.8.2 High-temperature combustion acid/base titration sul-
addition of sufficient gas absorption fluid as well as to the assembly of the fur analyzers may be designed to give a buret reading directly
apparatus. in percent sulfur content of the coal sample, but a correction

5
 D 4239 – 02a
still must be made for acidity caused by chlorine present in the METHOD B—HIGH-TEMPERATURE COMBUSTION
sample using Test Methods D 2361 or D 4208. METHOD WITH INFRARED ABSORPTION
PROCEDURE
NOTE 8—Often no correction is made for the presence of chlorine in the
sample, or a percentage value (found as a relatively invariant value based 10. Apparatus
upon prior knowledge of the coals being analyzed) is subtracted from the
10.1 Measurement Apparatus—Equipped to combust the
percent sulfur determined. This method can be acceptable for coals of
known chlorine content; however, for work of the highest accuracy, the sample as described in 3.2 automatically.
percentage of chlorine present in the sample must be determined analyti- 10.2 Tube Furnace—See 6.1.
cally, and correction for its presence made by subtracting an equivalent 10.3 Combustion Tube—Made of mullite, porcelain, or
value from a value equivalent to the total acidity determined by the sulfur zircon with provisions for routing the gasses produced by
titration. combustion through the infrared cell.
10.4 Sample Combustion Boats—See 6.4.
9. Calculations 10.5 Boat Puller—See 6.5.
9.1 Some sulfur analyzers are designed to give buret read- 11. Reagents
ings in percent sulfur if the titrant is adjusted and standardized
11.1 Purity of Reagents—See 7.1.
to exactly 0.05N and the sample weight is exactly 0.500 g.
11.2 Magnesium Perchlorate—(Warning—Magnesium
After the observed percent sulfur has been adjusted using the
perchlorate is a strong oxidizing agent. Do not try to regenerate
recovery factor or calibration curve, then it must be corrected
the absorbent. Do not allow contact with organic materials or
for chlorine using the following calculation: reducing agents.)
Sc 5 1.603 ~Sb/1.603 3 F 2 Cl, %/3.546! (2) 11.3 Oxygen—See 7.8.
11.4 Certified Reference Materials, such as SRM Nos. 2682
where: through 2685—Sulfur in Coal,6 reference coals or calibrating
Sc = sulfur corrected for chlorine (as determined), %;
agents with certified dry-basis sulfur values must be used. The
Sb = sulfur from buret reading, %;
F = the recovery factor or factor taken from a calibra- materials must be supplied by or have traceability to interna-
tion curve for the analyzer; and tionally recognized certifying organizations, such as the Na-
Cl, % = chlorine in sample (as determined), %. tional Institute of Standards and Technology.
11.4.1 All certified reference materials, reference coals, or
9.2 On analyzers that are designed to give buret readings in
calibrating agents must have precision values of less than or
percent sulfur, but where the normality of the titrant or sample equal to method repeatability. Such certified reference materi-
weight may vary from that prescribed, the following calcula- als, reference coals, or calibrating agents must be stable with
tion must be used: respect to moisture and be pulverized to pass 100 % through a
Sc 5 1.603 @~Sb 3 N1 3 F 3 10! 2 Cl, %/3.546#/W (3) 0.250-mm (No. 60) USA Standard Sieve. Certified reference
materials, reference coals, or calibrating agents must be mixed
where: thoroughly before each use.
Sc = sulfur corrected for chlorine (as determined), %;
Sb = sulfur taken from buret reading, %; 12. Procedure
N1 = normality of the sodium hydroxide;
12.1 Instrument Preparation—Perform system update
F = recovery factor or factor taken from a calibration
checks in accordance with manufacturer’s instructions.
curve for the analyzer;
Cl,% = chlorine in sample (as determined), %; and 12.1.1 Balance Calibration—Calibrate internal balance in
W = weight of sample, g. accordance with manufacturer’s instructions.
12.2 Calibration of the Infrared Detection System—Select
9.3 When sulfur analyzers are used that have buret readings
certified reference materials, reference coals, or calibrating
in millilitres of titrant, the following calculation will apply: agents with known dry-basis sulfur values in the range of the
Sc 5 1.603 @~V1 3 N1 3 F! 2 Cl, %/ 3.546#/W (4) samples to be analyzed. For the initial calibration and periodic
verification of instrument linearity, at least three such certified
where: reference materials, reference coals, or calibrating agents are
Sc = sulfur corrected for chlorine (as determined), %;
recommended for each range of sulfur values to be tested.
Sb = sulfur taken from buret reading, %;
V1 = sodium hydroxide, mL; When performing a single-point calibration (Note 9) the
N1 = normality of sodium hydroxide; certified reference materials, reference coal, or calibrating
Cl, % = chlorine in sample (as determined), %; agent containing the highest sulfur value for the expected range
F = the recovery factor or factor taken from a calibra-
tion curve for the analyzer; and 6
Available from the Office of Standard Reference Materials, Room B314,
W = weight of sample, g. Chemistry Bldg., National Bureau of Standards, Washington, DC 20234.

6
 D 4239 – 02a
should be used for calibration. The other two certified reference the certified reference materials, reference coals, or calibrating agents used
materials, reference coals, or calibrating agents should repre- for calibration and the samples to be analyzed should be approximately the
sent the low and midpoints of the expected range. When same so that both materials produce about the same amount of infrared
cell saturation (60 to 70 %).
performing a multiple point calibration, two of the certified
reference materials, reference coals, or calibrating agents 12.2.3 Periodic Calibration Verification—On a periodic
should bracket the range of sulfur values to be tested with the basis, verify the stability of the instrument and its calibration
third falling within the range. All results obtained must be by analyzing a portion of the certified reference materials,
within the allowable limits of the certified reference materials, reference coal, or calibrating agent used to calibrate the
reference coals, or calibrating agents. Records for all calibra- instrument. The value determined for this material, when used
tions will be maintained in accordance with Guide D 4621. as an unknown sample, must be within the certified value plus
12.2.1 All certified reference materials, reference coals, or or minus the stated precision limits of the material. If the
calibrating agents used for calibrating the instrument should criteria for a successful verification of calibration in accor-
comply with the provisions of 11.4. (Warning—An indicated dance with Test Method D 4621 is not met, the calibration
problem with linearity of the instrument during calibration procedure of 12.2.1 must be repeated and samples analyzed
could result from contamination of the certified reference since the last successful verification must be repeated.
material, reference coal, or calibrating agent as the container 12.3 Analysis Procedure—Stabilize and calibrate the ana-
becomes depleted. It is, therefore, suggested that extreme care lyzer (see 12.2).
be used in mixing the certified reference material, reference 12.3.1 Raise the furnace temperature as recommended by
coal, or calibrating agent before removing any sample from the the manufacturer to at least 1350°C. Weigh the sample (Note
container and that it be discarded when less than 5 g remain in 11). Spread the sample evenly in a combustion boat and use a
the container. boat puller to position the sample in the hot zone of the furnace
for at least 2 min (Note 12) or until completely combusted.
NOTE 9—When performing a single-point calibration, the technique of
calibrating the instrument with the certified reference materials, reference NOTE 12—The analytical cycle should begin automatically as soon as
coal, or calibrating agent corresponding to the highest sulfur value sulfur is detected.
expected for the range uses the optimum linear range available for
12.3.2 When the analysis is complete, the instrument should
calibration. Single-point calibration is most linear from the point of
calibration to zero. indicate the sulfur value. Refer to the manufacturer’s recom-
mended procedure.
12.2.2 Calibration Procedure—Make a minimum of two
determinations to condition the equipment before calibrating 13. Report
the system. The as-determined sulfur value of the certified 13.1 The percent sulfur value obtained using any of the
reference material, reference coal, or calibrating agent used for described methods is on an as-determined basis.
calibration of the instrument must have been previously 13.2 The results of the sulfur analysis may be reported on
calculated from the certified dry-basis sulfur value and residual any of a number of bases, differing from each other in the
moisture determined using either Test Methods D 3173 or manner by which moisture is treated.
D 5142. Alternately, a quantity of the certified reference 13.3 Use the percentage of moisture in the sample passing a
material, reference coal, or calibrating agent allocated to be No. 60 (250-µm) sieve to calculate the as-determined results of
used within a normal production period (Note 10) can be dried the analysis sample to a dry basis.
using either Test Methods D 3173 or D 5142, in which case, 13.4 Procedures for converting the value obtained on the
the dry basis sulfur value will be used. The dried material must analysis sample to other bases are described in Practices
be stored in a desiccator, and any remaining at the end of the D 3176 and D 3180.
normal production period must be discarded. Weigh five
samples of the certified reference material, reference coal, or 14. Precision and Bias
calibrating agent (Note 11) chosen to represent the range of
14.1 Precision—250mm (No.60) Samples.7 The precision
sulfur values being tested. Follow the calibration procedure
of this method for the determination of Sulfur in the analysis
recommended by the manufacturer. For verification of the
sample of coal and coke is shown in Table 1. The precision
calibration curve, use certified reference materials, reference
coals, or calibrating agents that bracket the range of values to
be tested. All results obtained must be within the allowable TABLE 1 Repeatability and Reproducibility for Acid Base
limits of the certified reference materials, reference coals, or Detection
calibrating agents. Records for all calibrations will be main- Range Repeatability Limit (r) Reproducibility Limit (R)
tained in accordance with Test Method D 4621. 0.5–6.0 0.06 + 0.03 X A
0.03 + 0.11 X A

A
NOTE 10—A normal production period would routinely be considered where X is the average of two single test results.
an 8-h shift. Dried certified reference materials, reference coals, or
calibrating agents should not be maintained beyond one day for the
purposes of instrument calibration. (Warning—Previously dried material
should not be redried as oxidation can readily occur.) 7
An interlaboratory study, designed consistent with ASTM Practice E 691, was
NOTE 11—Weigh to the nearest 1.0 mg. Since the sulfur content of the conducted in 1999. Twelve laboratories participated in this study.Supporting data
certified reference materials, reference coals, or calibrating agents bracket have been filed at ASTM International Headquarters and may be obtained by
the range of sulfur values being determined from the samples, the mass of requesting Research Report RR: D05–1020 (60 mesh).

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 D 4239 – 02a
characterized by repeatability (Sr, r) and reproducibility (SR, mm (No.8) test units of coal reduced entirely to 250 mm (No.
R) is described in table A1 in the Annex A1. 60) and prepared from the same bulk sample coal in the same
14.1.1 Repeatability Limit (r)-the value below which the laboratory by the same operator using the same apparatus on
absolute difference between two test results calculated to a dry samples taken at random from a single quantity of homoge-
basis (Practice D3180) of separate and consecutive test deter- neous material, may be expected to occur with a probability of
minations, carried out on the same sample of 250 µm (No. 60) approximately 95%.
coal and coke in the same laboratory by the same operator 14.2.2 Reproducibility Limit (R)—the value below which
using the same apparatus on samples taken at random from a the absolute difference between two test results calculated to a
single quantity of homogeneous material, may be expected to dry basis (Practice D3180) carried out in different laboratories
occur with a probability of approximately 95%. using samples of 2.36 mm (No. 8) coal reduced entirely to 250
14.1.2 Reproducibility Limit (R)—the value below which mm (No. 60) taken at random from a single quantity of
the absolute difference between two test results carried out in material that is as homogeneous as possible, may be expected
different laboratories using samples of 250 µm (No. 60) coal to occur with a probability of approximately 95%.
and coke taken at random from a single quantity of material 14.3 Bias— Bias eliminated when the instrument is prop-
that is as homogeneous as possible, may be expected to occur erly calibrated against certified reference standards. Proper
with a probability of approximately 95%. calibration includes comparison of instrumental results to
14.2 36 µm (No.8) samples:8 certified sulfur values. Results for certified standards above and
14.2.1 Repeatability Limit (r)—the value below which the below anticipated analysis sample results should be within
absolute difference between two test results calculated to a dry certified precision levels for all standards over the calibration
basis (Practice D3180) of separate and consecutive test deter- range for the instrument.
minations, carried out on the same sample, using the same
riffle, determined on a single test specimen of two separate 2.36 TABLE 2 Repeatability and Reproducibility for Infrared
Absorption Detection
Coal Range Repeatability Reproducibility
8
An interlaboratory study, designed consistent with Practice E 691, was Limit (r) Limit (R)
conducted in 1989. Eight laboratories participated in this study. Supporting data Bituminous 0.02 – 0.03% 0.05% 0.09%
have been filed at ASTM International Headquarters and may be obtained by Subbituminous Lignite 0.3 – 1.6 % 0.8 % 0.13 %
requesting Research Report RR: D05–1015 (8 mesh).

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 D 4239 – 02a

ANNEX

A1. Precision Statistics

A1.1 The precision of this test method, characterized by TABLE A1.1 Repeatability (Sr) and Reproducibility (SR)
repeatability (Sr, r) and reproducibility (SR, R) has been Parameters for Calculation of Precision Statement
determined for the following materials as listed in Table A1.1. Material Average Sr SR r R
91–2lvb 0.38775 0.011373 0.0248 0.031822 0.06939
91–1hvAb 1.24325 0.014004 0.030572 0.039183 0.08554
A1.2 Repeatability standard deviation (Sr),-the standard 91–5hvAb 3.083 0.028888 0.060704 0.080829 0.16985
deviation of test results obtained under repeatability condi- 89–4hvCb 5.6125 0.080452 0.209299 0.225106 0.58562
91–4hvCb 0.27725 0.018384 0.025722 0.051439 0.07197
tions.
90–1subB 1.442 0.015066 0.044989 0.042155 0.12588
89–7subA 0.75475 0.019184 0.028152 0.053677 0.07877
A1.3 Reproducibility standard deviation (SR)-the standard 91–6subA 0.46825 0.023578 0.021137 0.06597 0.05914
89–6subC 0.5235 0.016595 0.023399 0.046433 0.06547
deviation of test results obtained under reproducibility Lignite 0.666 0.210 0.0415 0.058622 0.11605
conditions.

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 D 4239 – 02a

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