Designation: D 4239 00

Standard Test Methods for

Sulfur in the Analysis Sample of Coal and Coke Using High-
Temperature Tube Furnace Combustion Methods
1
This standard is issued under the xed 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
1.1 These test methods cover three alternative procedures
using high-temperature tube furnace combustion methods for
the rapid determination of sulfur in samples of coal and coke.
1.2 These test methods appear in the following order:
Sections
Method AHigh-Temperature Combustion Method with Acid
Base Titration Detection Procedures 6-9
Method BHigh-Temperature Combustion Method with Iodi-
metric Titration Detection Procedures 10-13
Method CHigh-Temperature Combustion Method with Infra-
red Absorption Detection Procedures 14-16
1.2.1 When automated equipment is used to perform any of
the three methods of this test method, the procedures can be
classied as instrumental methods. There are several manufac-
turers that offer to the coal industry equipment with instrumen-
tal analysis capabilities for the determination of the sulfur
content of coal and coke samples.
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 appro-
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. See 7.8 and 15.2.
2. Referenced Documents
2.1 ASTM Standards:
D 346 Practice for Collection and Preparation of Coke
Samples for Laboratory Analysis
2
D 1193 Specication for Reagent Water
3
D 2013 Method of Preparing Coal Samples for Analysis
2
D 2361 Test Method for Chlorine in Coal
2
D 3173 Test Method for Moisture in the Analysis Sample of
Coal and Coke
2
D 3176 Practice for Ultimate Analysis of Coal and Coke
2
D 3180 Practice for Calculating Coal and Coke Analyses
from As-Determined to Different Bases
2
D 4208 Test Method for Total Chlorine in Coal by the
Oxygen Bomb Combustion/Ion Selective Electrode
Method
2
D 4621 Guide for Quality Management in an Organization
that Samples or Tests Coal and Coke
2
D 5142 Test Methods for the Proximate Analysis of the
Analysis Sample of Coal and Coke by Instrumental
Procedures
2
3. Summary of Test Methods
3.1 Method AHigh-Temperature Combustion Method with
Acid-Base Titration Detection ProceduresA weighed sample
is burned in a tube furnace at a minimum operating temperature
of 1350C in a stream of oxygen. During combustion, all sulfur
contained in the sample is oxidized to gaseous oxides of sulfur
(sulfur dioxide, SO
2
, and sulfur trioxide, SO
3
) and the chlorine
in the sample is released as Cl
2
. These products are then
absorbed into a solution of hydrogen peroxide (H
2
O
2
) where
they dissolve forming dilute solutions of sulfuric (H
2
SO
4
) and
hydrochloric (HCl) acids. The quantities of both acids pro-
duced are directly dependent upon the amounts of sulfur and
chlorine present in the original coal sample. Once the amounts
of each acid present have been determined, the percentage of
sulfur contained in the coal may be calculated.
3.1.1 This method is written to include commercially avail-
able sulfur analyzers that must be calibrated with appropriate
standard reference materials (SRMs) to establish recovery
factors or a calibration curve based on the range of sulfur in the
coal or coke samples being analyzed.
NOTE 1Elements ordinarily present in coal do not interfere in Method
A (3.1), with the exception of chlorine; results must be corrected for
chlorine content of the samples (9.1).
3.2 Method BHigh-Temperature Combustion Method with
Iodimetric Detection ProceduresA weighed sample is
burned in a tube furnace at a minimum operating temperature
of 1350C in a stream of oxygen to ensure the oxidation of
sulfur. The combustion products are absorbed in an aqueous
solution that contains iodine. When sulfur dioxide is scrubbed
by the diluent, the trace iodine originally present in the solution
is reduced to iodide, thus causing an increase in resistance. The
detection system of the instrument consists of a polarized dual
platinum electrode. Any change in resistance of the solution in
the vessel is detected. Iodine titrant is then added proportion-
ally to the reaction vessel until the trace excess of iodine is
1
This test method is under the jurisdiction of ASTM Committee D-5 on Coal and
Coke and is the direct responsibility of Subcommittee D05.21 on Methods of
Analysis.
Current edition approved April 10, 2000. Published July 2000. Originally
published as D 4239 83. Last previous edition D 4239 97
e1
.
2
Annual Book of ASTM Standards, Vol 05.06.
3
Annual Book of ASTM Standards, Vol 11.01.
1
Copyright ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.
replenished and the solution resistance is reduced to its initial
level. The volume of titrant expended is used to calculate the
sulfur concentration of the sample. The method is empirical;
therefore, the apparatus must be calibrated by the use of
standard reference material (SRM).
3.2.1 This method is designed to be used with commercially
available sulfur analyzers, equipped to perform the preceding
operation automatically, and must be calibrated with an appro-
priate sample (5.4) based on the range of sulfur in each coal or
coke sample analyzed.
NOTE 2Nonautomatic systems may be used with the titration proce-
dures and calculations performed manually by qualied laboratory tech-
nicians. The resulting loss in accuracy or speed, or both, would then
negate the advantages of using the fully automated instrumental approach.
3.3 Method CHigh-Temperature Combustion Method with
Infrared Absorption Detection ProceduresThe sample is
burned in a tube furnace at a minimum operating temperature
of 1350C in a stream of oxygen to oxidize the sulfur. Moisture
and particulates are removed from the gas by traps lled with
anhydrous magnesium perchlorate. The gas stream is passed
through a cell in which sulfur dioxide is measured by an
infrared (IR) absorption detector. Sulfur dioxide absorbs IR
energy at a precise wavelength within the IR spectrum. Energy
is absorbed as the gas passes through the cell body in which the
IR energy is being transmitted: thus, at the detector, less energy
is received. All other IR energy is eliminated from reaching the
detector by a precise wavelength lter. Thus, the absorption of
IR energy can be attributed only to sulfur dioxide whose
concentration is proportional to the change in energy at the
detector. One cell is used as both a reference and a measure-
ment chamber. Total sulfur as sulfur dioxide is detected on a
continuous basis. This method is empirical; therefore, the
apparatus must be calibrated by the use of SRMs.
3.3.1 This method is for use with commercially available
sulfur analyzers equipped to carry out the preceding operations
automatically and must be calibrated using standard reference
material (coal) of known sulfur content based on the range of
sulfur in each coal or coke sample analyzed.
4. Signicance and Use
4.1 Determination of sulfur is, by denition, part of the
ultimate analysis of coal.
4.2 Results of the sulfur analysis are used to serve a number
of interests: evaluation of coal preparation, evaluation of
potential sulfur emissions from coal combustion or conversion
processes, and evaluation of the coal quality in relation to
contract specications, as well as other scientic purposes.
4.3 The instrumental analysis provides a reliable, rapid
method for determining the concentration of sulfur in a lot of
coal or coke and are especially applicable when results must be
obtained rapidly for the successful completion of industrial,
beneciation, trade, or other evaluations.
5. Sample
5.1 The sample shall be the material pulverized to pass No.
60 (250-m) sieve and mixed thoroughly in accordance with
Method D 2013 or Practice D 346.
NOTE 3It may be difficult to meet the precision statements of Section
18 when high mineral content coals are ground to pass 60 mesh. When the
precision of analysis required cannot be obtained, it is recommended that
the coals be ground to pass through a No. 100 (150-m) sieve. The
reduced particle size should result in a more homogeneous sample.
5.2 A separate portion of the analysis sample should be
analyzed for moisture content in accordance with Test Method
D 3173, so that calculation to other than the as-determined
basis can be made.
5.3 Procedures for converting as-determined sulfur values
obtained from the analysis sample to other bases are described
in Practices D 3176 and D 3180.
5.4 Standard Reference Material (SRM) such as SRM Nos.
2682 through 2685Sulfur in Coal
4
which consist of four
different coals that have been individually crushed and ground
to pass a 60-mesh sieve, and bottled in 50-g units, or other
commercially available reference coals with a certied sulfur
content.
METHOD AHIGH-TEMPERATURE
COMBUSTION METHOD WITH ACID-BASE
TITRATION DETECTION PROCEDURES
5
6. Apparatus
6.1 Tube FurnaceCapable of heating 150- to 175-mm
area (hot zone) of the combustion tube (6.2) to at least 1350C.
It is usually heated electrically using resistance rods, a resis-
tance wire, or molybdenum disilicide elements. Specic di-
mensions may vary with manufacturers design.
NOTE 4Induction furnace techniques may be used provided it can be
shown that they meet the precision requirements of Section 18.
6.2 Combustion TubeApproximately 28-mm internal di-
ameter with a 3-mm wall thickness and 750 mm in length made
of porcelain, zircon, or mullite. It must be gastight at working
temperature. The combustion may be carried out in a tapered-
end tube that is closely connected to the gas absorber by
high-temperature tubing with gastight joints. Acceptable con-
gurations include connecting the tapered-end tube directly to
the elbow of the fritted gas bubbler or to a 10/30 standard
taper-ground joint that is attached to a heat-resistant glass right
angle bend. The temperature at the tapered end of the tube
should be maintained high enough to prevent condensation in
the tube itself.
6.2.1 Alternatively, a high-temperature straight refractory
tube may be used, if available. It requires a silica adaptor (6.11)
with a ared end that ts inside the combustion tube and serves
as an exit for the gases.
6.3 Flowmeter, for measuring an oxygen ow rate up to 2.0
L/min.
6.4 Sample Combustion Boats, must be made of iron-free
material and of a convenient size suitable for the dimensions of
the instrument being used.
4
Available from the Office of Standard Reference Materials, Room B314,
Chemistry Bldg., National Bureau of Standards, Washington, DC 20234.
5
Based on the method of Mott, R. A., and Wilkinson, H. C., Determination of
Sulfur in Coal and Coke by the Sheffield High Temperature Method, Fuel, Fuel B,
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
subjected to treatment with chlorinated hydrocarbons because of the potentially high
acidity of the combustion gases.
D 4239
2
6.5 Boat PullerRod of a heat-resistant material with a
bent or disk end to insert and remove boats from the combus-
tion tube.
6.5.1 If the boat puller is to remain within the combustion
tube while the boat is moved into the hot zone, it is necessary
to pass the puller through a T-piece that is tted into a rubber
stopper at the inlet of the combustion tube. The open end of the
T-piece is sealed with a rubber stopper to permit movement of
the pusher and prevent escape of the oxygen that enters at the
side limb of the T. The rubber stopper or tube should be
checked often to avoid leakage.
6.6 Gas Absorber or Analyzer Titration VesselA narrow
vessel of such diameter that the end of the tube from which the
gasses exit is inside the vessel and submerged to a depth of at
least 90 mm, when 200 mL of the peroxide solution (7.4) is
added to the vessel.
6.6.1 Alternatively, 125-mL capacity bottles with fritted
disk can be used for gas absorption. The bottles should be of
such a diameter that the fritted end is covered by the peroxide
solution to a depth of at least 50 mm. The fritted glass end
porosity should be 15 to 40 m. The bottles are tted in a series
of two to the outlet end of the combustion tube.
6.7 Gas-Purifying TrainDesigned to be used with specic
instruments, or a U-tube packed with soda asbestos may be
used. See conguration in Fig. 1.
6.8 Vacuum SourceNeeded if a negative pressure is used
to transport the gasses and combustion products through the
system.
6.9 Vacuum Regulating Bottle, containing mercury with an
open-ended tube dipping into the mercury, used with a vacuum
source.
6.10 Silica Adaptor, 300 mm long by 8 mm in outside
diameter and ared at one end to 26 mm. To be used with a
straight refractory combustion tube.
6.11 Other Congurations of ApparatusComplete sulfur
analyzer assembly units designed to perform functions similar
to this method with automated features that perform the sulfur
analysis in a more rapid manner are commercially available.
These instruments may have combustion tube dimensions and
oxygen-purifying apparatus that differ slightly from those
described in this method, but are acceptable, provided equiva-
lent values within the precision statement of Section 18 are
obtained. (See Fig. 2 and Fig. 3.)
7. Reagents
7.1 Purity of ReagentsReagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
all reagents shall conform to the specications of the Commit-
tee on Available Reagents of the American Chemical Society,
where such specications are available.
6
Other grades may be
used, provided it is rst ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
accuracy of the determination.
7.2 Purity of WaterUnless otherwise indicated, references
to water shall be understood to mean reagent water, Type IV,
conforming to Specication D 1193.
7.3 Aluminum Oxide (Al
2
O
3
)Finely divided and dried at
1350C.
7.4 Hydrogen Peroxide (H
2
O
2
) SolutionOne volume per-
cent (50 mL of 30 % H
2
O
2
with 1450 mL of water). The pH is
adjusted (using NaOH or H
2
SO
4
as appropriate) to that which
is used for the end point in the titration. Solutions should be
discarded after two or three days.
7.5 IndicatorIndicators that change color (titration end
point) between pH 4 and 5 are recommended, but in no case
should the pH exceed 7. Adequate lighting and stirring to
ensure proper detection of the end point is essential. A choice
of indicators or use of a pH meter is permitted (Note 5).
Directions for preparing two acceptable mixed indicators are as
follows:
7.5.1 Mix one part methyl red solution (dissolve 0.125 g in
60 mL of ethanol and dilute to 100 mL with water) with three
parts bromcresol green solution (dissolve 0.083 g in 20 mL of
ethanol and dilute to 100 mL with water). Discard the mixed
solution after one week.
7.5.2 Mix equal volumes of methyl red solution (dissolve
0.125 g in 60 mL of ethanol and dilute to 100 mL with water)
and methylene blue solution (dissolve 0.083 g in 100 mL of
ethanol and store in a dark glass bottle). Discard the mixed
solution after one week.
6
Reagent Chemicals, American Chemical Society Specications, 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
D 4239
3
NOTE 5Although two end-point indicators or a pH meter method are
described, the use of the pH meter is accepted as more denitive of the end
point of the titration process and considered to give more reproducible
results.
7.6 Soda-Asbestos, 8 to 20 mesh, if a U-tube is used.
7.7 Sodium Hydroxide, Standard Solution, 0.05NDissolve
2.05 g of sodium hydroxide (NaOH) in water and dilute to 1 L.
Standardize against a primary standard.
7.8 Oxygen, 99.5 % PureCompressed gas contained in a
cylinder equipped with a suitable pressure regulator and a
needle valve to control gas ow. (WarningPure oxygen
vigorously accelerates combustion. All regulators, lines, and
valves should be free of grease and oil.)
8. Procedure
8.1 Assemble the apparatus, as directed, by the instructions
of the instrument manufacturer. Alternatively, the apparatus
shown in Fig. 1 can be assembled except do not initially
connect the rubber tube from the oxygen supply to the soda
asbestos U-tube.
8.2 CalibrationSulfur analyzers must be calibrated at
least once on each day they are used, following the analysis
procedure outlined in Section 8, using coal or coke standards
(5.4) with sulfur values in the range of the samples being
analyzed. A recovery factor (F) or calibration curve must be
established and appropriately used in each calculation.
F 5
Actual Sulfur in Standard, Dry Basis
Analyzed Sulfur in Standard, Dry Basis
(1)
8.3 Furnace AdjustmentRaise the temperature of the fur-
nace to at least 1350C. Bring the temperature up slowly,
allowing approximately 3 to 4 h in advance, to allow sufficient
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
D 4239
4
time to come to a stable temperature. Be sure to check the
manufacturers instructions for raising the temperature of the
furnace and heed any precautions for protecting heating
elements from deterioration or thermal shock.
8.4 Titration Vessel PreparationFill the titration vessel in
accordance with the manufacturers instructions with approxi-
mately 200 mL of the gas absorption uid (hydrogen peroxide)
(7.4). Adjust the pH of the solution to make it denitely acidic
by adding dilute sulfuric acid. If chemical indicators (instead of
a pH meter) are used, add ve or six drops of the indicator and
then add a very small quantity (as required) of dilute sodium
hydroxide (NaOH) to reach the end point color that will be
developed in the sulfur analysis.
8.4.1 If the apparatus with two gas absorption bottles is
used, add 100 mL of 1 % H
2
O
2
(7.4) to the bottles so that at
least 50 mm of the fritted disk is covered in the rst bottle.
8.5 Oxygen FlowConnect the oxygen supply and adjust
the oxygen ow to approximately 2 L/min with the oxygen
baffle inserted in the entrance end of the combustion tube. Be
sure to check manufacturers instructions. The ow rate at the
temperature of 1350C should be sufficient to prevent the
formation of oxides of nitrogen. Allow the oxygen to ow
through the combustion tube for at least 1 min before inserting
any sample. Check the system for any possible leaks.
8.5.1 If a vacuum source is used, draw air through the
apparatus at about 350 mL/min, then connect the oxygen
supply to the U-tube and adjust the rate of ow of the oxygen
to 300 mL/min. The ow rate is adjusted by changing the depth
of the penetration into the mercury of the open-ended glass
tube in the vacuum regulating bottle. The preliminary adjust-
ment to 350 mL/min of air ensures that the connections at the
outlet end of the combustion tube are under slightly reduced
internal pressure and no leak of combustion products should
occur.
NOTE 6A gastight combustion train must be established with an
adequate ow of approximately 300 mL/min of pure acid-free oxygen
before analyzing samples on the equipment. This is best accomplished
during the period the high-temperature tube furnace is brought to its
operating temperature of 1350C. The required gas ow may be estab-
lished by the use of reduced internal pressure, or should the manufacturer
specify or the operator prefer, it can be obtained by the use of a positive
pressure train operated at slightly above atmospheric pressure to obtain the
required oxygen ow rate. In all cases, the instructions of the manufac-
turer of the equipment should be followed. This also applies to the
addition of sufficient gas absorption uid as well as to the assembly of the
apparatus.
8.6 Analysis Sample SizeWeigh out 0.5 g of the analysis
sample to the nearest 0.1 mg for coals containing up to 4.0 %
sulfur and 0.25 g to the nearest 0.1 mg of analysis sample for
coals containing over 4.0 % sulfur. Spread the sample evenly in
a combustion boat.
8.6.1 A thin layer of Al
2
O
3
can be used to line the sample
boat and cover the sample to ensure complete combustion and
reduce splattering or loss of sample.
8.7 Sample CombustionRemove the oxygen baffle or
rubber stopper or both from the combustion tube and put the
charged sample boat into the inlet end of the combustion tube
approximately 270 mm from the center of the combustion tube
hot zone. Close the combustion tube by replacing the oxygen
baffle or rubber stopper or both and, if necessary, readjust the
rate of ow of the oxygen. Leave the boat in this position for
1 to 3 min until the volatiles have been driven off. This will
also eliminate the popping and soot accumulation in the right
angle bend. Remove the oxygen baffle or rubber stopper and
move the sample boat slowly forward until the boat is in the
center of the hot zone, approximately 30 mm at the beginning
of each minute for 6 min is the suggested schedule to ensure a
slow heating rate. Be sure to remove the boat puller from the
hot zone and replace the baffle or stopper after each movement.
Allow the sample to burn in the hot zone for approximately 3
to 4 min until all sulfur in the sample is oxidized to sulfur
dioxide (SO
2
) or sulfur trioxide (SO
3
). The complete sample
burning time is not more than 14 to 15 min. This heating
program has been established for all types of coal. Where it is
shortened for a particular coal or by instruction of the manu-
facturer of a particular sulfur analyzer, results should be
checked against those obtained by using the longer heating
schedule.
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
and the boat puller is permitted movement into the furnace
through the T-piece. See Fig. 1.
8.8 TitrationThe gasses of combustion leave the combus-
tion tube through the exit end and are dissolved in the hydrogen
peroxide in the gas absorption bottles or analyzer titration
vessel forming a dilute sulfuric acid. Titrate the contents of this
vessel with 0.05N sodium hydroxide (7.7), backwashing the
titration vessel and inlet tubes according to manufacturers
instructions. The total acidity, because of oxides of sulfur and
chlorine, is given according to the following reactions:
SO
2
+ H
2
O
2
H
2
SO
4
Cl
2
+ H
2
O
2
2HCl + O
2
8.8.1 If the contents of the gas absorption bottles must be
transferred to a suitable titration ask, be sure to wash the
bottles and inlet tube or silica adaptor with water (7.2) and add
these washings and ve or six drops of indicator to the titration
ask before titrating with the 0.05N NaOH solution (7.7).
8.8.2 High-temperature combustion acid/base titration sul-
fur analyzers may be designed to give a buret reading directly
in percent sulfur content of the coal sample, but a correction
still must be made for acidity caused by chlorine present in the
sample using Test Methods D 2361 or D 4208.
NOTE 7Often no correction is made for the presence of chlorine in the
sample, or a percentage value (found as a relatively invariant value based
upon prior knowledge of the coals being analyzed) is subtracted from the
percent sulfur determined. This method can be acceptable for coals of
known chlorine content; however, for work of the highest accuracy, the
percentage of chlorine present in the sample must be determined analyti-
cally, and correction for its presence made by subtracting an equivalent
value from a value equivalent to the total acidity determined by the sulfur
titration.
9. Calculations
9.1 Some sulfur analyzers are designed to give buret read-
ings in percent sulfur if the titrant is adjusted and standardized
to exactly 0.05N and the sample weight is exactly 0.500 g.
After the observed percent sulfur has been adjusted using the
recovery factor or calibration curve, then it must be corrected
D 4239
5
for chlorine using the following calculation:
S
c
5 1.603 ~S
b
/1.603 3 F 2 Cl, %/3.546! (2)
where:
S
c
5 sulfur corrected for chlorine (as determined), %;
S
b
5 sulfur from buret reading, %;
F 5 the recovery factor or factor taken from a calibra-
tion curve for the analyzer; and
Cl, % 5 chlorine in sample (as determined), %.
9.2 On analyzers that are designed to give buret readings in
percent sulfur, but where the normality of the titrant or sample
weight may vary from that prescribed, the following calcula-
tion must be used:
S
c
5 1.603 @~S
b
3 N
1
3 F 3 10! 2 Cl, %/3.546#/W (3)
where:
S
c
5 sulfur corrected for chlorine (as determined), %;
S
b
5 sulfur taken from buret reading, %;
N
1
5 normality of the sodium hydroxide;
F 5 recovery factor or factor taken from a calibration
curve for the analyzer;
Cl,% 5 chlorine in sample (as determined), %; and
W 5 weight of sample, g.
9.3 When sulfur analyzers are used that have buret readings
in millilitres of titrant, the following calculation will apply:
S
c
5 1.603 @~V
1
3 N
1
3 F! 2 Cl, %/ 3.546#/W (4)
where:
S
c
5 sulfur corrected for chlorine (as determined), %;
S
b
5 sulfur taken from buret reading, %;
V
1
5 sodium hydroxide, mL;
N
1
5 normality of sodium hydroxide;
Cl, % 5 chlorine in sample (as determined), %;
F 5 the recovery factor or factor taken from a calibra-
tion curve for the analyzer; and
W 5 weight of sample, g.
METHOD BHIGH-TEMPERATURE COMBUSTION
METHOD WITH IODIMETRIC TITRATION
DETECTION
PROCEDURES
10. Apparatus
10.1 Analytical ApparatusDesigned to perform the analy-
sis procedure described in 3.2 automatically.
NOTE 8It is recommended that the analytical equipment be an
automated sulfur analyzer. Otherwise, the restrictions and limitations
given in Note 3 for nonautomated systems apply.
10.2 Tube FurnaceSee 6.1.
10.3 Combustion TubeMade of mullite, porcelain, or
zircon, approximately a 27-mm inner diameter, a 33-mm outer
diameter, and 750 mm in length, with the last 23 mm of the exit
end reduced to 10-mm outer diameter and 5-mm inner diameter
to facilitate exit and collection of the gases in the titration
vessel.
10.4 Sample Combustion BoatsSee 6.4.
10.5 Boat PullerSee 6.5.
11. Reagents
11.1 Purity of ReagentsSee 7.1.
11.2 Purity of WaterSee 7.2.
11.3 Iodine TitrantDissolve 2.5 g of iodine in 280 mL of
pyridine. Mix well and be certain all iodine is dissolved. Add
700 mL of methanol and 20 mL of water. (See Note 9.)
11.4 DiluentMix 280 mL of pyridine with 700 mL of
methanol and 20 mL of water. Mix well.
NOTE 9Alternative formulations may be substituted to the extent that
they can be demonstrated to yield equivalent results in regard to accuracy
and precision.
11.5 OxygenSee 7.8.
12. Procedure
12.1 Instrument Preparation:
12.1.1 Assemble the analytical apparatus according to the
manufacturers instructions. Check all connections carefully to
avoid leaks.
12.1.2 Set furnace temperature to 1350C.
12.1.3 Set oxygen ow rate according to manufacturers
instructions.
12.1.4 Place approximately 150 mg of a coal sample in a
boat and insert into the 1350C region of the furnace. Sample
boat should remain within the hot zone of the furnace for at
least 2 min or until sample is completely burned. This action
will serve to condition the apparatus in all functions.
12.2 Calibration:
12.2.1 Select a coal standard reference material (SRM), as
described in 5.4, which has a sulfur value in the range of the
sample to be analyzed. Weigh out about 150 mg of this
previously dried coal standard and record the weight to the
nearest 0.1 mg.
12.2.2 Enter the weight and sulfur content of the standard
reference material sample into the memory of the analyzer.
12.2.3 Insert SRM sample into the 1350C region of the
furnace.
12.2.4 After endpoint is reached, not less than 2 min, record
the titrant factor as milligrams sulfur per millilitre of titrant
(mgS/mL). If analyzer does not have an integral computer,
record the volume of titrant used and calculate titrant factor as
instructed in 13.1.
12.2.5 Remove sample boat and repeat Steps 12.2.1-12.2.4
two more times.
12.2.6 If analyzer does not automatically average the titrant
factors obtained in the calibration step and enter the average
into the microprocessor, then do so manually. Successive
calibrations should yield titrant factors within 0.01 mgS/mL of
each other.
12.3 Analysis Procedure:
12.3.1 Use an instrument that has been conditioned and
calibrated according to 12.1 and 12.2.
12.3.2 Weigh to the nearest 0.1 mg, approximately 150 mg
of the coal analysis sample into a boat.
12.3.3 Enter the sample weight into the sulfur analyzer
memory.
12.3.4 Insert the coal sample into the 1350C region of the
furnace.
12.3.5 After the endpoint is reached (not less than 2 min),
record the sulfur concentration of the sample. If analyzer does
not have an integral computer, record the volume of titrant used
D 4239
6
and calculate the sulfur concentration as instructed in 13.2.
13. Calculations
13.1 On analyzers that do not calculate the titrant factor
automatically, the following calculation must be used:
T 5 S
s
3 W/100 3 V
t
(5)
where:
T 5 titrant factor, mg of sulfur/mL;
S
s
5 sulfur concentration of standard, dry basis;
W 5 weight of standard, mg; and
V
t
5 volume of titrant, mL.
13.2 On analyzers that do not calculate the percent sulfur in
the analysis sample automatically, the following calculation
must be used:
S 5 100 ~T 3 V
t
!/W (6)
where:
S 5 percent sulfur (as determined),
T 5 titrant factor (see 13.1),
V
t
5 volume of titrant, mL, and
W 5 weight of sample, mg.
METHOD CHIGH-TEMPERATURE COMBUSTION
METHOD WITH INFRARED ABSORPTION
PROCEDURE
14. Apparatus
14.1 Measurement ApparatusEquipped to combust the
sample as described in 3.3 automatically. (See Note 8.)
14.2 Tube FurnaceSee 6.1.
14.3 Combustion TubeMade of mullite, porcelain, or
zircon with provisions for routing the gasses produced by
combustion through the infrared cell.
14.4 Sample Combustion BoatsSee 6.4.
14.5 Boat PullerSee 6.5.
15. Reagents
15.1 Purity of ReagentsSee 7.1.
15.2 Magnesium Perchlorate(WarningMagnesium
perchlorate is a strong oxidizing agent. Do not try to regenerate
the absorbent. Do not allow contact with organic materials or
reducing agents.)
15.3 OxygenSee 7.8.
15.4 Standard Reference Material (SRM)Such as SRM
Nos. 2682 through 2685Sulfur in Coal,
4
reference coals or
calibrating agents with certied dry-basis sulfur values must be
used. The materials must be supplied by or have traceability to
internationally recognized certifying organizations, such as the
National Institute of Standards and Technology.
15.4.1 All SRMs, reference coals, or calibrating agents must
have precision values of less than or equal to method repeat-
ability. Such SRMs, reference coals, or calibrating agents must
be stable with respect to moisture and be pulverized to pass
100 % through a 0.250-mm (No. 60) USA Standard Sieve.
SRMs, reference coals, or calibrating agents must be mixed
thoroughly before each use.
16. Procedure
16.1 Instrument PreparationPerform system update
checks in accordance with manufacturers instructions.
16.1.1 Balance CalibrationCalibrate internal balance in
accordance with manufacturers instructions.
16.2 Calibration of the Infrared Detection SystemSelect
SRMs, reference coals, or calibrating agents with known
dry-basis sulfur values in the range of the samples to be
analyzed. For the initial calibration and periodic verication of
instrument linearity, at least three such SRMs, reference coals,
or calibrating agents are recommended for each range of sulfur
values to be tested. When performing a single-point calibration
(Note 10) the SRM, reference coal, or calibrating agent
containing the highest sulfur value for the expected range
should be used for calibration. The other two SRMs, reference
coals, or calibrating agents should represent the low and
midpoints of the expected range. When performing a multiple
point calibration, two of the SRMs, reference coals, or cali-
brating agents should bracket the range of sulfur values to be
tested with the third falling within the range. All results
obtained must be within the allowable limits of the SRMs,
reference coals, or calibrating agents. Records for all calibra-
tions will be maintained in accordance with Guide D 4621.
16.2.1 All SRMs, reference coals, or calibrating agents used
for calibrating the instrument should comply with the provi-
sions of 15.4. (WarningAn indicated problem with linearity
of the instrument during calibration could result from contami-
nation of the SRM, reference coal, or calibrating agent as the
container becomes depleted. It is, therefore, suggested that
extreme care be used in mixing the SRM, reference coal, or
calibrating agent before removing any sample from the con-
tainer and that it be discarded when less than 5 g remain in the
container.
NOTE 10When performing a single-point calibration, the technique of
calibrating the instrument with the SRM, reference coal, or calibrating
agent corresponding to the highest sulfur value expected for the range uses
the optimum linear range available for calibration. Single-point calibration
is most linear from the point of calibration to zero.
16.2.2 Calibration ProcedureMake a minimum of two
determinations to condition the equipment before calibrating
the system. The as-determined sulfur value of the SRM,
reference coal, or calibrating agent used for calibration of the
instrument must have been previously calculated from the
certied dry-basis sulfur value and residual moisture deter-
mined using either Test Methods D 3173 or D 5142. Alter-
nately, a quantity of the SRM, reference coal, or calibrating
agent allocated to be used within a normal production period
(Note 11) can be dried using either Test Methods D 3173 or
D 5142, in which case, the dry basis sulfur value will be used.
The dried material must be stored in a desiccator, and any
remaining at the end of the normal production period must be
discarded. Weigh ve samples of the SRM, reference coal, or
calibrating agent (Note 12) chosen to represent the range of
sulfur values being tested. Follow the calibration procedure
recommended by the manufacturer. For verication of the
calibration curve, use SRMs, reference coals, or calibrating
agents that bracket the range of values to be tested. All results
obtained must be within the allowable limits of the SRMs,
D 4239
7
reference coals, or calibrating agents. Records for all calibra-
tions will be maintained in accordance with Test Method
D 4621.
NOTE 11A normal production period would routinely be considered
an 8-h shift. Dried SRMs, reference coals, or calibrating agents should not
be maintained beyond one day for the purposes of instrument calibration.
(WarningPreviously dried material should not be redried as oxidation
can readily occur.)
NOTE 12Weigh to the nearest 1.0 mg. Since the sulfur content of the
SRMs, reference coals, or calibrating agents bracket the range of sulfur
values being determined from the samples, the mass of the SRM,
reference coals, or calibrating agents used for calibration and the samples
to be analyzed should be approximately the same so that both materials
produce about the same amount of infrared cell saturation (60 to 70 %).
16.2.3 Periodic Calibration VericationOn a periodic
basis, verify the stability of the instrument and its calibration
by analyzing a portion of the SRM, reference coal, or calibrat-
ing agent used to calibrate the instrument. The value deter-
mined for this material, when used as an unknown sample,
must be within the certied value plus or minus the stated
precision limits of the material. If the criteria for a successful
verication of calibration in accordance with Test Method
D 4621 is not met, the calibration procedure of 16.2.1 must be
repeated and samples analyzed since the last successful veri-
cation must be repeated.
16.3 Analysis ProcedureStabilize and calibrate the ana-
lyzer (see 16.2).
16.3.1 Raise the furnace temperature as recommended by
the manufacturer to at least 1350C. Weigh the sample (Note
12). Spread the sample evenly in a combustion boat and use a
boat puller to position the sample in the hot zone of the furnace
for at least 2 min (Note 13) or until completely combusted.
NOTE 13The analytical cycle should begin automatically as soon as
sulfur is detected.
16.3.2 When the analysis is complete, the instrument should
indicate the sulfur value. Refer to the manufacturers recom-
mended procedure.
17. Report
17.1 The percent sulfur value obtained using any of the
described methods is on an as-determined basis.
17.2 The results of the sulfur analysis may be reported on
any of a number of bases, differing from each other in the
manner by which moisture is treated.
17.3 Use the percentage of moisture in the sample passing a
No. 60 (250-m) sieve to calculate the as-determined results of
the analysis sample to a dry basis.
17.4 Procedures for converting the value obtained on the
analysis sample to other bases are described in Practices
D 3176 and D 3180.
18. Precision and Bias
18.1 These are empirical methods that are highly dependent
upon the calibration of the equipment, the closeness of the
standards to the samples in sulfur content, chlorine content,
iron content, and so forth.
18.2 Precision Statement for High-Temperature Combustion
Method Using Acid Base Titration Detection ProceduresThe
relative precision of this method for the determination of total
sulfur covers the concentration range from 0.5 to 6.0 %.
18.2.1 RepeatabilityThe difference in absolute value be-
tween two consecutive test results carried out on the same
sample of 60-mesh pulp, in the same laboratory, by the same
operator, using the same apparatus, should not exceed the
repeatability interval I(r) more than 5 % of such paired values
(95 % condence level). When such a difference is found to
exceed the repeatability interval, there is reason to question one
or both of the test results. The repeatability interval may be
calculated by use of the following equation:
I~r! 5 0.06 1 0.03 x (7)
where x is the average of the two test results.
NOTE 14This equation applies to the relative spread of a measure-
ment that is expressed as a percentage and is derived from the statistical
evaluation of the round-robin analytical results. Example: Duplicate
analysis for total sulfur gave values of 1.52 and 1.57 %. The average
sulfur of the duplicate analysis value is 1.55 % and the calculated
repeatability I(r) is 0.11. The difference between the two sulfur values is
0.05 and does not exceed the I(r) of 0.11; therefore, these two values are
acceptable at the 95 % condence level.
18.2.2 ReproducibilityThe difference in absolute value
between the averages of replicate determinations, carried out in
different laboratories on representative 60-mesh samples, pre-
pared from the same bulk sample after the last stage of
reduction, should not exceed the reproducibility interval I(R)
more than 5 % of such paired values (95 % condence level).
When such a difference is found to exceed the reproducibility
interval, there is reason to question one, or both, of the test
results. The reproducibility interval may be calculated by the
use of the following equation:
I~R! 5 0.03 1 0.11 x (8)
where x is the average of between-laboratory results.
NOTE 15This equation applies to the relative spread of a measure-
ment that is expressed as a percentage and is derived from the statistical
evaluation of the round-robin analytical results. Example: Duplicate
analysis for total sulfur in one laboratory gave an average value of 3.81 %,
and a value of 4.00 % was obtained in a different laboratory. The
between-laboratory average sulfur value is 3.91 %, the calculated I(R)
interval is 0.46 %, and the difference between the different laboratory
values is 0.19 %. Since this difference is less than the I(R), these two
values are acceptable at the 95 % condence level.
18.3 Precision Statement for High-Temperature Combustion
Method Using Iodimetric Detection ProceduresThe relative
precision of this method for the determination of total sulfur
covers the concentration range from 0.5 to 6.0 %.
18.3.1 RepeatabilityThe difference in absolute value be-
tween two consecutive test results carried out on the same
sample of 60-mesh pulp, in the same laboratory, by the same
operator, using the same apparatus should not exceed the
repeatability interval I(r) more than 5 % of such paired values
(95 % condence level). When such a difference is found to
exceed the repeatability interval, there is reason to question
one, or both, of the test results. The repeatability interval may
be determined by use of the following equation:
I~r! 5 0.08 x (9)
where x is the average of the two test results.
D 4239
8
NOTE 16This equation applies to the relative spread of a measure-
ment that is expressed as a percentage and is derived from the statistical
evaluation of the round-robin analytical results. Example: Duplicate
analysis for total sulfur gave values of 1.52 and 1.57 %. The average
sulfur of the duplicate analysis value is 1.55 %, and the calculated
repeatability interval I(r) is 0.12. The difference between the two sulfur
values is 0.05 and does not exceed the I(r) of 0.12; therefore, these two
values are acceptable at the 95 % condence level.
18.3.2 ReproducibilityThe difference in absolute value
between the averages of replicate determinations, carried out in
different laboratories on representative 60-mesh samples pre-
pared from the same bulk sample after the last stage of
reduction, should not exceed the reproducibility interval I(R)
more than 5 % of such paired values (95 % condence level).
When such a difference is found to exceed the reproducibility
interval, there is reason to question one, or both, of the test
results. The reproducibility interval may be determined by use
of the following equation:
I~R! 5 0.08 1 0.09 x (10)
where x is the average of the between-laboratory results.
NOTE 17This equation applies to the relative spread of a measure-
ment that is expressed as a percentage and is derived from the statistical
evaluation of the round-robin analytical results. Example: Duplicate
analysis for total sulfur in one laboratory gave an average value of 3.81 %,
and a value of 4.00 % was obtained in a different laboratory. The
between-laboratory average sulfur value is 3.91 %, the calculated I(R)
interval is 0.43 %, and the difference between the different laboratory
values is 0.19 %. Since this difference is less than the I(R), these two
values are acceptable at the 95 % condence level.
18.4 Precision Statement for High-Temperature Combustion
Method Using Infrared Absorption Detection Procedures:
18.4.1 Precision250-m (No. 60) SamplesThe relative
precision of this test method for the determination of sulfur
covers the concentration range from 0.28 to 5.61 %.
18.4.1.1 RepeatabilityThe difference in absolute value
between two consecutive test results, carried out on the same
sample in the same laboratory by the same operator using the
same apparatus, should not exceed the repeatability interval
(limit) I(r) more than 5 % of such paired values (95 %
condence level). When such a difference is found to exceed
the repeatability interval (limit), there is reason to question one
or both of the test results. The repeatability interval on a dry
basis may be determined by use of the following equation:
I~r! 5 0.02 1 0.03 x (11)
where x is the average of the two test results (see Note 18).
18.4.1.2 ReproducibilityThe difference in absolute value
of replicate determinations, carried out in different laboratories
on representative samples prepared from the same bulk sample
after the last stage of reduction, should not exceed the
reproducibility interval (limit) I(R) more than 5 % of such
paired values (95 % condence level). When such a difference
is found to exceed the reproducibility interval (limit), there is
reason to question one or both of the test results. The
reproducibility interval on a dry basis may be determined by
use of the following equation:
I~R! 5 0.02 1 0.09 x (12)
where x is the average of the two test results (see Note 18).
NOTE 18These equations apply to the relative spread of a measure-
ment that is expressed as a percentage as derived from a statistical
evaluation of the round-robin results.
18.4.2 Precision2.36-mm (No. 8) SamplesThe relative
precision of this test method for determination of sulfur covers
the concentration range from 0.2 to 3.0 % for bituminous coals
and 0.3 to 1.6 % for subbituminous and lignite coals.
18.4.2.1 RepeatabilityThe difference in absolute value
between test results obtained in the same laboratory, by the
same operator, using the same apparatus, determined on a
single test specimen of two separate 2.36mm (No. 8) test units
of coal reduced entirely to 250m (No. 6) and prepared from
the same bulk sample, should not exceed the repeatability
interval for more than 5 % of such paired values (95 %
condence level). When such a difference is found to exceed
the repeatability interval, there is reason to question one or
more of the test results. The repeatability interval for this
method is as follows:
Bituminous coals 0.05 %
Subbituminous and lignite coals 0.08 %
18.4.2.2 ReproducibilityThe difference in absolute value
between test results obtained in laboratories calculated as the
average of determinations on single test specimens of two
separate 2.36mm (No. 8) test units of coal reduced entirely to
250m (No. 60) and prepared from the same bulk sample,
should not exceed the reproducibility interval for more than
5 % of such paired values (95 % condence level). When such
a difference is found to exceed the reproducibility interval,
there is reason to question one or more of the test results. The
reproducibility interval for this test method is as follows:
Bituminous coals 0.09 %
Subbituminous and lignite coals 0.13 %
NOTE 19Supporting data for 2.36mm (No. 8) coal has been led at
ASTM Headquarters and may be obtained by requesting RR: D051015.
18.5 BiasBias is eliminated when the instrument is prop-
erly calibrated against certied reference standards. Proper
calibration includes comparison of instrumental results to
certied sulfur values. Results for certied standards above and
below anticipated analysis sample results should be within
certied precision levels for all standards over the calibration
range for the instrument.
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D 4239
9
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D 4239
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