Designation: D 5468 02

Standard Test Method for

Gross Calorific and Ash Value of Waste Materials1

This standard is issued under the fixed designation D 5468; 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.

3.1.1 calorific valuethe heat produced by combustion of a

unit quantity of a specimen under specified conditions. It is
expressed in this test method in joules per kilogram (J/kg).
Calorific value may also be expressed in calories per gram
(cal/g) or in the British thermal units per pound (Btu/lb), when
required. The unit equivalents are given in Table 1.
3.1.2 calorimeteras used in this test method, is not only
the bomb and its contents, but it also includes the bucket,
electronic temperature sensing devices, ignition leads, water,
and stirrer when using water.
3.1.2.1 adiabatic calorimetera calorimeter that has a
jacket temperature adjusted to follow the calorimeter temperature as closely as possibly so as to maintain zero thermal head.
3.1.2.2 calorimeter jacketthe insulating medium surrounding the calorimeter.
3.1.2.3 isoperibol calorimeterthe calorimeter has a jacket
of uniform and constant temperature.
3.1.3 gross calorific value (gross heat of combustion), Qv
(gross)the heat produced by combustion of unit quantity of
a solid or liquid fuel when burned at constant volume in an
oxygen bomb calorimeter under specified conditions with the
resulting water condensed to a liquid.
3.1.4 heat capacitythe quantity of heat required to raise a
system one degree in temperature either at constant volume or
constant pressure.
3.1.5 heat of formationthe increase in heat content resulting from the formation of 1 mole of a substance from its
elements at constant pressure.
3.1.6 net calorific value (net heat of combustion at constant
pressure), Qpthe heat produced by combustion of unit
quantity of a solid or liquid fuel when burned at a constant
pressure of 0.1 MPa (1 atm), under conditions such that all the
water in the products remain in the form of vapor.
3.1.7 static calorimetera calorimeter without a thermostated jacket.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 corrected temperature risethe temperature of the
calorimeter caused by the process that occurs inside the bomb,
which is, the observed temperature change corrected for
various effects.
3.2.2 heat capacity, energy equivalent, or water
equivalentthe energy required to raise the temperature of the
calorimeter one arbitrary unit. This is the quantity that, when

1. Scope
1.1 This test method covers the determination of the gross
calorific value of waste materials by either an isoperibol,
aneroid, air-jacketed isoperibol, or adiabatic bomb calorimeter
using electronic temperature sensors, automatic calorimeter
controllers, and subsequent analysis of the residue for ash.
After calorific analysis, the bomb washings may be collected
for subsequent elemental analysis.
1.2 The values stated in SI units are regarded as the
standard.
1.3 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Specific hazard
statements are given in Section 8.
2. Referenced Documents
2.1 ASTM Standards: 2
D 121 Terminology of Coal and Coke
D 240 Test Method for Heat of Combustion of Liquid
Hydrocarbon Fuels by Bomb Calorimeter
D 1018 Test Method for Hydrogen in Petroleum Fractions
D 1193 Specification for Reagent Water
D 3177 Test Method for Total Sulfur in the Analysis Sample
of Coal and Coke
D 4239 Test Method for Sulfur in the Analysis Sample of
Coal and Coke Using High Temperature Tube Furnace
Combustion Methods
E 144 Practice for Safe Use of Oxygen Combustion Bombs
3. Terminology
3.1 Definitions:

1
This test method is under the jurisdiction of ASTM Committee D34 on Waste
Management and is the direct responsibility of Subcommittee D34.03.02 on
Municipal Recovery and Reuse.
Current edition approved May 10, 2002. Published July 2002. Originally
published as D 5468 93. Last previous edition D 5468 95.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standards Document Summary page on
the ASTM website.

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

D 5468 02
TABLE 1 Calorific Value
1 Btu = 1055.06 J
1 calA = 4.1868 J
A

component or integral component of the bomb. It shall be of

such construction that the environment of the calorimeters
entire outer boundaries is maintained at a uniform temperature.
6.5 JacketAn insulated container that keeps the inner
perimeter of the jacket at constant temperature (isoperibol), or
at the same temperature as the calorimeter (adiabatic), or is
monitored continuously for temperature changes (aneroid).
6.6 Temperature Sensing DeviceThermometers such as
platinum resistance, thermistors, or mercurial thermometers are
satisfactory and may be used if properly calibrated.

1 J/g = 0.430 Btu/lb

1 J/g = 0.239 cal/g

International tables calorie.

multiplied by the corrected temperature, rises, then when

adjusted for extraneous heat effects and divided by the mass of
the sample, gives the gross calorific value.
4. Summary of Test Method
4.1 Calorific value is determined in this test method by
burning a weighed sample under controlled conditions, in
oxygen, in a calibrated calorimeter. The calorimeter is standardized by burning a specified amount of benzoic acid. The
calorific value of the test specimen is computed from temperature observations made before, during, and after combustion
and making proper allowances for heat contribution by other
processes.
4.2 After disassembly of the bomb, estimate the ash content
by one of two of the following procedures:
4.2.1 Dry the fuel capsule at 200C for 5 to 10 min and
weigh to provide an estimation of the ash content of the waste
material.
4.2.2 Wipe any moisture from the exterior surface of the
capsule and weigh to provide an estimation of the ash content
of the waste material.

NOTE 1Temperature is measured in either degrees Celsius, degrees

Fahrenheit, ohms, or other arbitrary units instead of degrees. Consistent
units must be used in standardization and the actual calorific value
determination.

6.7 Sample Holder An open crucible of platinum, quartz,

or acceptable base-metal alloy. The base metal crucibles should
be heat-treated for 24 h at 500C to ensure the capsules are
completely oxidized.
6.8 Ignition Fuse The ignition fuse shall be 100 mm of
0.16-mm diameter or smaller (No. 34 B & S gage), nickelchromium alloy (Chromel C) alloy, platinum, cotton thread, or
iron wire. The same length or mass of ignition fuse shall be
used for all calibrations and calorific value determinations.
6.9 Firing Circuit A 6 to 24-V alternating or direct current
is required for ignition purposes. A step-down transformer
connected to an alternating current lighting circuit, capacitors,
or batteries may be used.
6.10 BuretUsed for the acid titration and shall have 0.1
mL divisions.
6.11 Gelatin Capsules or Cellulose TapeUsed to minimize vaporization of volatile samples. These items should be
halogen free.
6.12 pH Titrators or mV MetersMay be used for pH
titration of wash solution.

5. Significance and Use

5.1 This test method is used to compute the calorific value
and estimated ash content of the waste material represented by
the sample for incineration purposes or as fuel for cement
kilns.
5.2 The gross calorific and ash value may be used for
evaluating the effectiveness of any beneficiation process.

7. Reagents
7.1 Reagent Water Conforming to conductivity requirements for Type II of Specification D 1193, it shall be used for
preparation of reagents and washing of the bomb interior.
7.2 Purity or ReagentsReagent-grade chemicals conforming to the specifications of the Committee on Analytical
Reagents of the American Chemical Society shall be used in all
tests.3
7.3 Benzoic Acid, Standard (C6H5COOH)Use pellets
made from benzoic acid available from the National Institute of
Standards and Technology (NIST) or benzoic acid calibrated
against NIST standard material. The value of heat of combustion of benzoic acid, for use in the calibrations calculations,
shall be in accordance with the certified value.
7.4 Methyl Orange, Methyl Red, or Methyl Purple
IndicatorMay be used to titrate the acid formed during

6. Apparatus and Facilities

6.1 Test RoomA room or area free from drafts and that can
be kept at a constant temperature equal to 6 3C, for all
calorimetric tests. The apparatus shall be shielded from direct
sunlight and radiation from other sources. Thermostatic control
of room temperature and controlled relative humidity are
desirable.
6.2 Combustion Bomb Constructed of materials that are
not affected by the combustion process or products sufficiently
to introduce measurable heat input or alteration of end products. The bomb shall be designed so that all liquid combustion
products can be completely recovered by washing the inner
surfaces. There shall be no gas leakage. The bomb shall be
capable of withstanding a hydrostatic pressure test of 20 MPa
(3000 psig) at room temperature without stressing any part
beyond its elastic limit.
6.3 BalanceA laboratory balance having the capability to
weight the sample to the nearest 0.0001 g. The balance shall be
checked for accuracy at the beginning of each week that the
calorimeter tests will be made.
6.4 Calorimeter Vessel (Bucket)Made of metal with a
tarnish-resistant coating, with all outer surfaces highly polished. For calorimeters having a bucket it may be a separate

3
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
MD.

D 5468 02
9. Sampling
9.1 The sample shall be representative of the material of
interest (see Appendix X3).

combustion. The indicator used shall be the same for both

calibration and calorific value determinations.
7.5 OxygenShall be free of combustible matter. Only
oxygen manufactured from liquid air, guaranteed to be greater
than 99.5 % pure, shall be used. Oxygen made by the electrolytic process may contain a small amount of hydrogen,
rendering it unfit without purification by passage over copper
oxide at 500C.
7.6 Standard SolutionSodium carbonate (Na2CO3) or
other suitable standard solution. Dissolve 3.76 g of sodium
carbonate that has been dried for 24 h at 105C in water and
dilute to 1 L. One millilitre of this solution is equivalent to 4.2
J (1.0 cal) in the acid titration when the entire rinse solution is
used as the analytical sample. Alternatively, the titrant volume
is to be corrected by the volume fraction of the rinse that is
used as the analytical sample. (See 10.4.2.)

10. Standardization
10.1 The calorimeter is standardized by combustion of
benzoic acid.
10.2 Determine heat capacity as the average of a minimum
of 6 individual runs made over a period of not less than 3 days
nor more than 5 days. To be acceptable for highprecision work,
the relative standard deviation of the series shall be 0.15 % or
less. See Table 2. For users of static-type calorimeters, an
acceptable relative standard deviation would be 0.40 % or less.
For this purpose, any individual test may be discarded only if
there is evidence of incomplete combustion. If this limit is not
met, the entire series shall be repeated until a series is obtained
with a relative standard deviation below the acceptable limit.
10.3 Procedure:
10.3.1 Control the mass of the pellets of benzoic acid in
each calibration series to obtain the same temperature rise as
obtained with the waste specimen tested in the same laboratory.
Weigh the pellet during the same test day and to the nearest
0.0001 g in the sample holder in which it is to be burned, and
record the weight.
10.3.2 Rinse the bomb with water to lubricate internal seals
and dry surfaces. Add approximately 1 mL of water or desired
amount of other appropriate solution (see Note 2) to the bomb
prior to assembly for a test.

8. Hazards
8.1 The following precautions are recommended for safe
calorimeter operation. Additional precautions are given in
Practice E 144. Also consult the calorimeter equipment manufacturers installation and operating instructions before using
the calorimeter.
8.2 The mass of waste sample and the pressure of the
oxygen admitted to the bomb must not exceed the bomb
manufacturers recommendations.
8.3 Inspect the bomb parts carefully after each use. When
halogenated organic compounds are being tested, replace all
O-rings and valve seats after 100 firings. If no halogenated
organic compounds are being tested, replace all O-rings and
valve seats after 500 firings. At least every 3000 firings, check
the bomb for thread wear on any closures or return to the
manufacturer for these tests. These are recommendations for
worst case situations. For more details, contact the manufacturer.
8.4 Equip oxygen supply cylinder with an approved type of
safety device, such as a reducing valve, in addition to the
needle valve and pressure gage used in regulating the oxygen
feed to the bomb. Valves, gages, and gaskets must meet
industry safety codes. Suitable reducing valves and adapters
for 3 to 4-MPa (300 to 500-psi) discharge pressure are
obtainable from commercial sources of compressed gas equipment. Check the pressure gage annually for accuracy or after
any accidental over pressures that reach maximum gage
pressure.
8.5 During ignition of a sample, the operator must not
permit any portion of the operators body to extend over the
calorimeter.
8.6 Exercise extreme caution not to exceed the bomb
manufacturers recommendations and to avoid damage to the
bomb when combustion aids are employed. Do not fire loose
fluffy material, such as unpelleted benzoic acid, unless thoroughly mixed with the sample.
8.7 Do not fire the bomb if the bomb has been dropped or
turned over after loading or if there is evidence of gas leakage
when the bomb is submerged in the calorimeter water.
8.8 When volatile materials are present, explosive firings
can result and the procedure in 12.2 should be followed.

NOTE 2If the washing will be used for elemental analysis, then add 5
mL of a 10 % sodium carbonate solution or other solution of desired
amount rather than 1 mL of water to the bomb prior to assembly for both
standardization and analysis procedures.

10.3.3 Connect a measured fuse to the ignition terminals, in

accordance with the manufacturers guidelines. (See 6.8.)
10.3.4 Assemble the bomb and charge it with oxygen to a
consistent pressure of 3 MPa (30 atm). Lower charging
pressures may be used if they will not result in incomplete
combustion as evident by visual inspection for carbon residues
TABLE 2 Standard Deviations for Calorimeter Standardization

NOTE 1Average = X = 10253.5.

NOTE 2Variance =
Sum Column C 2 [~Sum Column B!2/n] 5 26.34
.
n21
3Standard Deviation = s = =variance = =237.1 = 5.14.
s2 5

NOTE

Standardization
Number
1
2
3
4
5
6
7
8
9
10
SUM

Column A

Column B

Column C

Energy Equivalent,
J/C

Difference from
Average

(Column B)2

10257.7
10249.3
10270.2
10253.5
10245.1
10249.3
10240.9
10266.0
10257.7
10245.1

4.2
4.2
16.7
0
8.4
4.2
12.6
12.5
4.2
8.4

17.6
17.6
278.9
0
70.6
17.6
158.8
156.3
17.6
70.6

75.4

805.6

D 5468 02
fuel capsule. Titrate the washings with standard solution as
defined under reagents, or titrate with pH meter.
10.3.7 Use the manufacturer recommended constant value
or remove and measure, or weigh, the combined pieces of
unburned ignition (firing) wire and subtract from the original
length or weigh to determine the wire consumed in firing. If the
wire is weighed, remove the ball of oxidized metal from the
end of each piece of wire before weighing. When cotton thread
fuse is used, use the manufacturers recommended calorie
correction.
10.4 Calculations:
10.4.1 Temperature Rise Where applicable use data obtained as prescribed in 10.3.5; compute the corrected temperature rise, t, as follows:

or the formation of carbon monoxide rather than carbon

dioxide. This pressure must remain the same for each calibration and each calorific value determination. Admit the oxygen
slowly into the bomb so as not to blow powdered material from
the sample holder. If the pressure exceeds the specified
pressure, detach the filling connection and exhaust the bomb in
the usual manner, then discard the sample and bucket of water.
Transfer the bucket, bomb, and calorimeter water to the jacket.
Finish assembly of the apparatus and start the calorimeter. The
calorimeter initial water temperature shall be at the same
temperature 60.5C for every determination. The calorimeter
monitors and determines whether the calorimeter has been
constant over a period of 30 s. For adiabatic calorimeters with
microprocessor control this stability requirement is 103C,
and it is 10 3C/s or better for the isoperibol calorimeter with
microprocessor control.

t 5 tc 2 t a 1 Cr

(1)

where:
t = corrected temperature rise, C (F),
ta = initial temperature reading at time of firing,
tc = final temperature reading, and
Cr = radiation correction (see A1.1.3).
10.4.2 Thermochemical Corrections (see Appendix X1)
Compute the following for each test:

NOTE 3The initial temperature adjustment will ensure a final temperature slightly below that of the jacket for isoperibol calorimeters.

10.3.5 Temperature Observations:

10.3.5.1 Observations (Extrapolation Method)The controller will fire the charge, record the temperature rise, and
correct the temperature rise for any appropriate heat leak
corrections as recommended or defined, or both, by the
instrument manufacturer. The controller may terminate the test
when the observed thermal curve matches the manufacturers
thermal curve, which allows extrapolation to a final temperature. The extrapolated temperature rise should have a maximum uncertainty of 6 0.002C.
10.3.5.2 Observations (Full Development Method)The
controller will fire the bomb and record the temperature rise
until the temperature has stabilized for a period of 30 s.
10.3.5.3 Manual Full Development MethodFire the
charge at time a and record this temperature as ta. For adiabatic
calorimeters record subsequent readings at intervals no greater
than 1 min until the difference between 3 or more pairs of
successive readings are the same. For isoperibol calorimeters
record the subsequent readings until the difference between 3
or more pairs of successive readings are the same within 1
millidegree per min. Record the time of stabilization as c and
the final temperature as tc, the first reading after the rate of
change has become uniform.
10.3.6 Open the cover and remove the bomb. Release the
pressure at a uniform rate, such that the operation will require
not less than 1 min. Open the bomb and examine the bomb
interior. Unburned samples or sooty deposits are indications of
incomplete combustion possibly due to highash content or
high-moisture content, or both. The results are suspect and
generally require combustion aid such as ethylene glycol for
water-based compounds or mineral oil for high-ash content
compounds. When combustion aids are used, be sure heat
liberation for any test meets the calorimeter manufacturers
guidelines. Discard the test if unburned sample or sooty
deposits are found. Use the manufacturers recommended
constant value for acid correction or wash the interior of the
bomb with distilled water containing the titration indicator
until the washings are free of acid. Rinse only the exterior of
the fuel capsule, taking care not to disturb the ash residue in the

e1 = correction for the heat of formation of HNO3, in

joules. Each millilitre of standard Na2CO3 is equivalent to 4.2 J (1.0 cal) and may be considered to be a
constant value as recommended by the calorimeter
manufacturer.
e2 = correction for heat of combustion of firing fuse, in
joules, or may be considered to be a constant value as
recommended by the calorimeter manufacturer.
e2 = 0.96 J/mm (0.23 cal/mm) or 5.9 J/mg (1.4 cal/mg) for
No. 34 B&S gage Chromel C.
e2 = 1.13 J/mm (0.27 cal/mm) or 7.5 J/mg (1.8 cal/mg) for
No. 34 B&S gage iron wire.
10.4.3 Compute the calorimeter heat capacity by substituting in the following:
E 5 [~H cm! 1 e1 1 e2#/t

(2)

where:
E = calorimeter heat capacity,
Hc = heat of combustion of benzoic acid, as stated in the
NIST Certificate, J/kg in air,
m = mass (weight in air) of benzoic acid, g,
e1 = titration correction (10.4.2),
e2 = fuse correction (10.4.2), and
t
= corrected temperature rise (10.4.1).
For sample calculations, see Appendix X4.
10.5 Repeat the procedure for a total of ten standardizations
or a minimum of six standardizations. Compute the standard
deviation as illustrated in Table 2. (The percent relative
standard deviation is the standard deviation times 100 and
divided by the average value.)
11. Restandardization
11.1 Make checks on the heat capacity value, after changing
any part of the bomb or calorimeter, at a minimum of at least
once a month.
4

D 5468 02
11.1.1 If a single new standardization differs from the old
energy equivalent value by 0.33 % of the heat capacity, the old
standard value is suspect, thereby requiring a second test.
11.1.2 The difference between the two new standardizations
must not exceed 0.23 % of the heat capacity, and the average of
the two new standardizations shall not differ from the old
standard by more than 6 0.25 % of the heat capacity. If these
requirements are met, do not change the calorimeter standard.
11.1.3 If the requirements given in 11.1.2 are not met, two
more standardizations must be run. The range of the four
values shall not exceed 0.35 % of the heat capacity, and the
average of the four new standardizations shall not differ from
the old standard value by more than 6 0.17 % of the heat
capacity. If these requirements are met, do not change the
calorimeter standard.
11.1.4 If the requirements given in 11.1.3 are not met, a fifth
and sixth standardization shall be run. The range of the six new
standardizations shall not exceed 0.44 % of the heat capacity,
and the average of the six values shall not differ from the old
standard by more than 60.17 % of the heat capacity. If these
requirements are met, do not change the calorimeter standard.
If the requirements are not met, use the new average of the last
six calibration tests.
11.2 The summary of the numerical requirements at each
stage of restandardization is given in Table 3. A similar table
may be configured for the static calorimeter by using a factor
of 2.7.

as a spiking agent. When using spiking agents or combustion aids, the

total amount of combustibles should meet the manufacturers guidelines.

12.2 Volatile compounds should be weighed in gelatin

capsules or in the sample holders, which are sealed with
halogen-free cellulose tape. Samples with metal particle content should be combusted in silica capsules.
12.3 Follow the bomb procedures and temperature observation procedures as described in 10.3.2-10.4.2 for standardization.
12.4 Remove the fuel capsule and dry on a hot plate. Weigh
the fuel capsule with ash residue on an analytical balance to
0.0001 g.
13. Calculation
13.1 Compute the corrected temperature rise, t, as shown in
10.4.1, where applicable. (See Note 1.)
13.2 Thermochemical Correction (Appendix X1)
Compute the following for each test:
e1

e2
e2

12. Procedure for Waste Samples (Note 4)

12.1 Weigh the Test SpecimenWeigh a representative
portion of waste and combustion aid as recommended by
calorimeter manufacture (minimum 0.4 g) to the nearest 0.1
mg.

e2
e3
e3

NOTE 4For waste samples which have high-ash or moisture content,

or both, or are ash samples that do not easily burn completely, one of the
following procedures are recommended. (1) The mass of the sample may
be varied to obtain good ignition. If the mass is varied, it will be necessary
to recalibrate the calorimeter so that the heat capacity will be based on the
same temperature rise as that obtained with the new sample weight. (2) A
known amount of benzoic acid may be mixed with the sample as a spiking
agent. Correction must be made for the calorific value of benzoic acid
when calculating the calorific value of the sample. (3) A known amount of
mineral oil, ethylene glycol, or other combustion aid may be mixed with
the sample. The amount of combustion aid will be dependent on the
completeness of combustion. Calorific value for the combustion aid must
be determined so as to make the necessary correction for the use of the aid

e4

= correction for the heat of formation of HNO3 (X1.2).

Each millimetre of standard sodium carbonate is
equivalent to 4.2 J (1 cal). This correction may be
considered to be a constant value.
= correction for heat of combustion of ignition fuse
(X1.3).
= 0.96 J/mm (0.23 cal/mm) or 5.9 J/mg (1.4 cal/mg) for
No. 34 B & S Chromel C Wire. This correction may
be considered to be a constant value.
= 1.13 J/mm (0.27 cal/mm) or 7.5 J/mg (1.8 cal/mg) for
No. 34 B & S gage iron wire.
= correction for difference between heat of formation of
H2SO 4 from the heat of formation of HNO3, J (X1.2).
= 55.2 J/g (13.17 cal/g) times percent of sulfur in
sample times sample mass (for additional information, refer to Test Methods D 3177 and D 4239)
= correction for use of spiking material, ethylene glycol, mineral oil, gelatin capsule, or tape = m
(g) 3 Hc(J/g).

14. Calorific Value (Note 4)

14.1 Gross Calorific ValueCalculations may be performed by a microprocessor, or one may calculate the gross
calorific value (gross heat of combustion at constant volume)
Qg(gross) as follows:
Qg ~gross! 5 [~tE! 2 e 1 2 e2 2 e3 2 e4#m

where:
Qg (gross)
t

TABLE 3 Summary of Numerical Requirements

= gross calorific value, J/kg,

= corrected temperature rise as calculated in
10.4.1,
E
= heat capacity calculated in 10.4.3,
e 1, e2, e3, e4 = corrections as described in 13.2, and
m
= mass of sample, g.
For sample of calculations, reference Appendix X4.
14.2 Net Calorific ValueCalculate the net calorific value
(net heat of combustion at a constant pressure), Qp (net) as
follows:

NOTE 1Test values exceeding table limits require additional runs.

NOTE 2X1 = average of original standard; X2 = average of check
runs.
Number of Runs

1
2
4
6

Maximum Range of
Maximum Difference
Results Relative to
Between X1 and X2 Relative
Systems Heat Capacity,
to Systems Heat Capacity, %
%
...
0.23
0.33
0.40

(3)

60.33
60.25
60.17
60.17

Qn ~net! 5 Qg ~gross! 2 0.2122H

(4)

D 5468 02
where:
Qn (net)
Qg (gross)
H

where:
r = weight of capsule and residue, g,
c = tare weight of capsule, g, and
g = mass of sample, g.

= net calorific value, MJ/kg,

= gross calorific value, MJ/kg, and
= total hydrogen, mass % (for additional information, refer to Test Method D 1018).
Net calorific value formulas are taken from Test Method
D 240.

16. Precision and Bias

16.1 Gross Calorific ValueRepeatability, reproducibility,
and bias data has not been determined at this time.
16.2 AshRepeatability, reproducibility, and bias data has
not been determined at this time.

NOTE 5This calculation gives calorific value in joules per kilogram.

To obtain calorific value in other units, see Table 1.

15. Ash
15.1 Estimated Ash ContentCalculations for estimated
ash content is calculated as follows:
% Ash 5 ~r 2 c!100/g

17. Keywords
17.1 ash; bomb calorimeters; calorific value; calorimeter;
isoperibol bomb calorimeter

(5)

ANNEX
(Mandatory Information)
A1. THERMOMETRIC CORRECTIONS
Cr 5 nr 1 1 kS

A1.1 Thermometer CorrectionsIt is necessary to make

the following individual corrections if not making the corrections would result in a heat capacity change of 11.3 J (2.7 cal)
or more:
A1.1.1 Calibration CorrectionShall be made in accordance with the calibration certificate furnished by the calibration authority.
A1.1.2 Radiation CorrectionsThese are used to calculate
heat loss to the water jacket. They are based on the Dickinson
formula,4 the Regnault-Pfaundler formula,5 or the U.S. Bureau
of Mines method.6 The same method of determining the
radiation correction must be used consistently in calibration
and test measurements.
A1.1.2.1 Dickinson Formula:
Cr 5 2r 1~b 2 a! 2 r2~c 2 b!

where:
Cr
n

(A1.2)

= radiation correction,
= number of minutes in the combustion
period,
k
= (r1 r2)/(t9 t8),
S
= tn 1 + (1/2)(ti + t f)n8,
t8
= average temperature during the preliminary period,
t9
= average temperature during the final period,
= see A1.1.2.1,
r1, r2
= successive temperature recorded during
t1, t2, t 3...tn
the combustion period, at 1-min intervals,
and
= sum of t1, t2, t3... tn 1.
tn 1
A1.1.2.3 Burea of Mines MethodA table of radiation
correction can be established so that only the initial and final
readings are required to determine the heat value of any fuel.
This may be done by carrying out a series of tests utilizing the
procedure described in Section 10, using the following conditions. Regulate the amount of sample burned so that a series of
determinations is made in which different temperature rises are
obtained. For all determinations, keep the water jacket temperature constant, fire the bomb at the same initial temperature,
and have the same time, c a, elapse (6 2 s) between the
initial and final readings. Determine the radiation corrections
for each of the series of temperature rises using the Dickinson
method (see A1.1.2.1), or the Regnault-Pfaundler method (see
A1.1.2.2). These corrections are constant for a given temperature rise. From the series of readings a table or graph is plotted
to show radiation correction versus temperature rise. Once the
table or graph is established, the radiation corrections can be
obtained from it until there is a major change in the equipment.

(A1.1)

where:
Cr = radiation correction,
r1 = rate of rise in temperature per minute in the preliminary period,
r2 = rate of rise of temperature per minute in the final
period (if temperature is falling, r2 is negative),
ta = firing temperature,
tc = final temperature, being the first temperature after
which the rate of change is constant,
a = time at temperature, ta, min,
b = time at temperature, ta + 0.60 (tc ta), min, and
c = time at temperature, tc, min.
A1.1.2.2 Regnault-Pfaundler Formula:

Dickinson, H. C., Bulletin, U.S. Bureau of Standards, Vol 11, 1951, p. 189.
Pfaundler, L., Annalen der Physik (Leipzig), ANPYA, Vol 129, 1966, p. 102.
6
Methods of Analyzing and Testing Coal and Coke, U.S. Bureau of Mines,
Bulletin 638, XMBUA, 1967, pp. 1617.
5

D 5468 02
APPENDIXES
(Nonmandatory Information)
X1. THERMOCHEMICAL CORRECTIONS

correction is 295.0 (2 3 59.0) = 177 kJ/mol, or 5.52

kJ/g of sulfur in the sample (55.2 J/g 3 weight of sample in
grams 3 percent sulfur in sample). This causes e3 to be 13.17
cal/g 3 weight of samples in grams 3 percent sulfur in
sample. The factor 23.7 Btu/g ( = 55.2/2.326 3 1.8) for e3 (see
13.2) is to be used for calculating calorific value in Btu/lb. The
values stated are based on a sample containing about 5 %
sulfur and about 5 % hydrogen. The assumption is also made
that the H2SO4 is dissolved entirely in the water condensed
during combustion of the sample.9
X1.2.1 If a 1-g sample is burned, the resulting H 2SO4
condensed with water formed on the walls of the bomb will
have a ratio of about 15 mol of water to 1 mol of H2SO 4. For
this concentration the energy of the reaction SO2 (g) + 12 O
2(g) + H2O (1) = H2SO 4 (in 15 mol of H2O) under the
conditions of the bomb process is 295 kJ/mol.9 For different
sample weights or sulfur content, or both, the resultant normality of acid formed may be significantly different, and
therefore the normality of titrant must be adjusted accordingly.
Basing the calculation upon a sample of comparatively large
sulfur content reduces the possible overall errors, because, for
small percentages of sulfur, the correction is smaller.

X1.1 Energy of Formation of Nitric AcidA correction, e1

(10.4.2 and 13.2) is applied for the acid titration. This correction is based on the assumptions (1) that all the acid titrated is
HNO3 formed by the following reaction: 12 N2 (g) + 34 O2
(g) + 12 H2O (I) = HNO 3 (in 500 mol H2O), and (2) that the
energy of formation of HNO3 in approximately 500 mol of
water under bomb conditions is minus 59.0 kJ/mol.7 Normal
convention assigns a negative value for a heat of formation that
is exothermic. By definition heat released from combustion
processes is expressed as a positive value. For conformity, the
negative factors developed for nitric and sulfuric acid corrections are expressed as positive values in the calculations.
X1.1.1 A convenient concentration of Na2CO 3 is 37.6 g
Na2CO3/1000 mL, which gives e1 = 10 3 V, where V is the
volume of Na 2CO3 in millilitres. When H2SO4 is also present,
a part of the correction for H2SO4 is also present in the e1
correction and the remainder in the e3 correction.
X1.2 Energy of Formation of Sulfuric AcidBy definition
(see Terminology D 121) the gross calorific value is obtained
when the product of the combustion of sulfur in the sample is
SO2(g). However, in actual bomb combustion processes, all the
sulfur is found as H2SO4 in the bomb washings. A correction e3
(see 13.2) is applied for the sulfur that is converted to H2SO4.
This correction is based upon the energy of formation of H2SO
4 in solutions, such as will be present in the bomb at the end of
a combustion. This energy is taken as 295.0 kJ/mol.8 When
nitric and sulfuric acid are present, a correction of 2 3 59.0
kJ/mol of sulfur was applied in the e1 correction so that the
additional correction that is necessary is the difference in the
heats of formation for nitric and sulfuric acid, and this
7
8

X1.3 Fuse (Ignition)Calculate the energy contributed by

burning the fuse in accordance with the directions furnished by
the supplier of the fuse. The energy required to melt a platinum
wire is constant for each experiment if the same amount of
platinum wire is used. As the energy is small, its effect is
essentially canceled out in the relationship between the standardization experiments and the calorific value determinations,
and it can be neglected.
9
Mott, R. A., and Parker, C., Studies in Bomb Calorimetry IXFormation of
Sulfuric Acid, Fuel, FUELB, Vol 37, 1958, p. 371.

Calculated from data in NBS Technical Note 270-3.

Calculated from data in NBS Circular 500.

X2. REPORTING RESULTS IN OTHER UNITS

X2.1 The gross calorific value can be expressed in joules

per kilogram, calorie per gram, or British thermal unit per

pound. The relationships between these units are given in Table

1.

D 5468 02

X3. SAMPLING INFORMATION

X3.1 SW-846 Test Methods for the Evaluation of Solid

Waste, Physical/Chemical Methods, or their equivalent.10
10
Available from the Superintendent of Documents, U.S. Government Printing
Office, Washington, DC 20402.

X4. SAMPLE CALCULATIONS

X4.2 Heat of CombustionCalculations from 14.1:

X4.1 Heat CapacityCalculation from 10.4.3:

E 5 [~Hcm! 1 e1 1 e 2#/t

Qg ~gross! 5 [~tE! 2 e 1 2 e2 2 e3 2 e4#/m

(X4.1)

where:
E
=
t
=
e1 =
e2 =
e3 =
e4 =
m
=
Qg =

where:
Hc =
m =
e1 =
e2 =
t
=
E =
E

6318 cal/g,
1.0047 g,
10.4 cal acid correction,
18.2 cal fuse correction,
2.542C,
[(6318 cal/g 3 1.0047 g) 10.4 cal 18.2 cal]/
2.6350C, and
= 2398.1 cal/C.

Qg

2398.1 cal/C
2.417C,
27.1 cal acid correction,
17.9 cal fuse correction,
13.17 3 1.24 % 3 0.7423 g sulfur correction,
11 000 cal/g 3 0.2043 g spike correction,
0.7423 g mass of sample,
[(2398.1 cal/C 3 2.417C) 27.1 cal 17.9
cal 12.1 cal 2247 cal (3492.11 cal]/0.7423 g),
and
= 4704.01 cal/g.

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(X4.2)