An American National Standard

Designation: D 4809 00

Standard Test Method for

Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb

Calorimeter (Precision Method)1
This standard is issued under the fixed designation D 4809; 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.
This standard has been approved for use by agencies of the Department of Defense.

D 1193 Specification for Reagent Water3

D 1266 Test Method for Sulfur in Petroleum Products
(Lamp Method)2
D 2622 Test Method for Sulfur in Petroleum Products by
Wavelength Dispersive X-Ray Fluorescence Spectrometry2
D 3120 Test Method for Trace Quantities of Sulfur in Light
Liquid Petroleum Hydrocarbons by Oxidative Microcoulometry2
D 3701 Test Method for Hydrogen Content of Aviation
Fuels by Low Resolution Nuclear Magnetic Resonance
Spectrometry4
D 4294 Test Method for Sulfur in Petroleum and Petroleum
Products by Energy Dispersive X-ray Fluorescence Spectroscopy4
D 5453 Test Method for Determination of Total Sulfur in
Light Hydrocarbons, Motor Fuels and Oils by Ultraviolet
Fluorescence5
E 1 Specification for ASTM Thermometers6
E 144 Practice for Safe Use of Oxygen Combustion
Bombs7
E 200 Practice for Preparation, Standardization, and Storage of Standard and Reagent Solutions for Chemical
Analysis8

1. Scope
1.1 This test method covers the determination of the heat of
combustion of hydrocarbon fuels. It is designed specifically for
use with aviation turbine fuels when the permissible difference
between duplicate determinations is of the order of 0.2 %. It
can be used for a wide range of volatile and nonvolatile
materials where slightly greater differences in precision can be
tolerated.
1.2 In order to attain this precision, strict adherence to all
details of the procedure is essential since the error contributed
by each individual measurement that affects the precision shall
be kept below 0.04 %, insofar as possible.
1.3 Under normal conditions, the method is directly applicable to such fuels as gasolines, kerosines, Nos. 1 and 2 fuel
oil, Nos. 1-D and 2-D diesel fuel and Nos. 0-GT, 1-GT, and
2-GT gas turbine fuels.
1.4 Through the improvement of the calorimeter controls
and temperature measurements, the precision is improved over
that of Test Method D 240.
1.5 The values stated in SI units are to be regarded as the
standard.
1.6 This standard does not purport to address the safety
concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and
health practices and determine the applicability of regulatory
limitations prior to use. For specific hazard statements, see
Section 7, 10.6, A1.7.1 and Annex A3.

3. Terminology
3.1 Definitions:
3.1.1 gross heat of combustionexpressed as megajoules
per kilogram. The gross heat of combustion at constant volume
of a liquid or solid fuel containing only the elements carbon,
hydrogen, oxygen, nitrogen, and sulfur is the quantity of heat
liberated when a unit mass of the fuel is burned in oxygen in
an enclosure of constant volume, the products of combustion
being gaseous carbon dioxide, nitrogen, sulfur dioxide, and
liquid water, with the initial temperature of the fuel and the

2. Referenced Documents
2.1 ASTM Standards:
D 129 Test Method for Sulfur in Petroleum Products (General Bomb Method)2
D 240 Test Method for Heat of Combustion of Liquid
Hydrocarbon Fuels by Bomb Calorimeter2
D 1018 Test Method for Hydrogen in Petroleum Fractions2

1
This test method is under the jurisdiction of ASTM Committee D-2 on
Petroleum Products and Lubricantsand is the direct responsibility of Subcommittee
D02.05on Petroleum, Coke, and Carbon Materials.
Current edition approved Dec. 10, 2000. Published January 2001. Originally
published as D 4809 88. Last previous edition D 4809 95.
2
Annual Book of ASTM Standards, Vol 05.01.

Annual
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Annual
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Annual
7
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Annual
4

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ASTM
ASTM
ASTM
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ASTM
ASTM

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

Standards,
Standards,
Standards,
Standards,
Standards,
Standards,

Vol
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Vol
Vol
Vol

11.01.
05.02.
05.03.
14.03.
14.04.
15.05.

D 4809 00
1 MJ/kg 5 1000 J/g

oxygen and the final temperature of the products at 25C.

Gross heat of combustion (see Note 1) is represented by the
symbol Q g.9

NOTE 3In SI the unit of heat of combustion has the dimension J/kg,
but for practical use a multiple is more convenient. The MJ/kg is
customarily used for the representation of heats of combustion of
petroleum fuels.

NOTE 1Users of this test method desiring to calculate D H for a pure

compound should note that corrections must be applied to the value of Qg
for buoyancy of air, heat capacities of reaction components, reduction to
a constant-pressure process, and deviations of the reaction from the
thermodynamic standard state. In any comparison of measurements on
pure compounds with those cited in these compilations9, the user of this
test method should realize that impurities of various kinds, including
water and foreign hydrocarbons may cause significant effects on the
values obtained for particular samples of material.

3.2.5 The following relationships may be used for converting to other units:
1
1
1
1

cal (International Table calorie) = 4.1868 JA

Btu (British thermal unit) = 1055.06 J
cal (I.T.)/g = 0.0041868 MJ/kgA
Btu/lb = 0.002326 MJ/kgA

Conversion factor is exact.

3.1.2 net heat of combustionexpressed as megajoules per

kilogram. The net heat of combustion at constant pressure of a
liquid or a solid fuel containing only the elements carbon,
hydrogen, oxygen, nitrogen, and sulfur is the quantity of heat
liberated when a unit mass of the fuel is burned in oxygen at a
constant pressure of 0.101 MPa (1 atm), the products of
combustion being carbon dioxide, nitrogen, sulfur dioxide, and
water, all in the gaseous state, with the initial temperature of
the fuel and the oxygen and the final temperature of the
products of combustion at 25C. The net heat of combustion10,11 is represented by the symbol Qn and is related to the
gross heat of combustion by the following equation:
Qn ~net, 25C! 5 Q g ~gross, 25C! 2 0.2122 3 H

(2)

4. Summary of Test Method

4.1 The heat of combustion is determined by burning a
weighed sample in an oxygen-bomb calorimeter under controlled conditions. The temperature increase is measured by a
temperature reading instrument which allows the precision of
the method to be met. The heat of combustion is calculated
from temperature observations before, during, and after combustion, with proper allowance for thermochemical and heattransfer corrections. Either isoperibol or adiabatic calorimeters
may be used.

(1)

5. Significance and Use

where:
Qn (net, 25C)

5.1 The heat of combustion is a measure of the energy

available from a fuel. A knowledge of this value is essential
when considering the thermal efficiency of equipment for
producing either power or heat.
5.2 The mass heat of combustion, that is, the heat of
combustion per unit mass of fuel, is measured by this procedure. Its magnitude is particularly important to weight-limited
vehicles such as airplanes, surface effect vehicles, and hydrofoils as the distance such craft can travel on a given weight of
fuel is a direct function of the fuels mass heat of combustion
and its density.
5.3 The volumetric heat of combustion, that is, the heat of
combustion per unit volume of fuel, can be calculated by
multiplying the mass heat of combustion by the density of the
fuel (mass per unit volume). The volumetric heat of combustion, rather than the mass heat of combustion, is important to
volume-limited craft such as automobiles and ships, as it is
directly related to the distance traveled between refuelings.

= net heat of combustion at constant

pressure, MJ/kg,
Q g (gross, 25C) = gross heat of combustion at constant
volume, MJ/kg, and
H
= mass % of hydrogen in the sample.
3.1.3 energy equivalent (effective heat capacity or water
equivalent)the energy equivalent of the calorimeter expressed as joules per degree Celsius, J/C.
NOTE 2The energy equivalent may be expressed in any energy unit
and any temperature unit so long as the value is used consistently
throughout the calculations.

3.2 Units:
3.2.1 Temperatures are measured in degrees Celsius.
3.2.2 Time is expressed in minutes and decimal fractions
thereof. It can be measured in minutes or seconds, or both.
3.2.3 Masses are measured in grams. No buoyancy corrections are applied except to obtain the mass of benzoic acid.
3.2.4 The energy unit of measurement employed in this test
method is the joule with the heat of combustion reported in
megajoules per kilogram (Note 3).

6. Apparatus
6.1 Test Room, Bomb, Calorimeter, Jacket, Thermometers,
and Accessories, as described in Annex A1.
6.2 Semimicro Analytical Balance, having a sensitivity of
0.01 mg as specified in 10.5.1.
6.3 Heavy-Duty Analytical Balance, having a sensitivity of
0.05 g as specified in 10.7.2.

9
Prosen, E. J., Experimental Thermochemistry. F. D. Rossini, editor, Interscience Publishers, 1956, pp. 129148. Reliable values for heats of combustion of
pure compounds are given in National Bureau of Standards Circular C-461,
Selected Values of Properties of Hydrocarbons (U.S. Government Printing Office,
Washington, DC, 1947) and in F. D. Rossini, et al, Selected Values of Physical and
Thermodynamic Properties of Hydrocarbons and Related Compounds, Carnegie
Press, Pittsburgh, PA, 1953. These compilations were prepared by F. D. Rossini, et
al, as part of American Petroleum Institute Research Project 44.
10
Derivation of equations has been filed at ASTM Headquarters. Request RR:
D021346.
11
See Jessup, R. S., Precise Measurement of Heat of Combustion with a Bomb
Calorimeter, NBS Monograph 7, U.S. Government Printing Office.

7. Reagents and Materials

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 specifications of the Committee on Analytical Reagents of the American Chemical Society,
2

D 4809 00
where such specifications are available.12 Other grades may be
used, provided it is first 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 conforming
to Specification D 1193, Type IV or better.
7.3 Benzoic Acid13The acid must be pelleted before use.
7.4 Firing Wire0.127 mm (No. 36 gage) platinum wire,
No. 34 B & S gage iron wire or Chromel C resistance wire, cut
in 100-mm lengths.
7.5 Methyl Red Indicator.
7.6 OxygenCommercial oxygen produced from liquid air
can be used without purification (WarningOxygen vigorously accelerates combustion. (See A3.1.)). Oxygen prepared
by electrolysis of water cannot be used without purification as
it can contain some hydrogen. Combustible impurities may be
removed by passage over copper oxide at 500C.
7.7 Pressure-Sensitive TapeCellophane tape 38 mm (112
in.) wide, free of chlorine and sulfur.14
7.8 Alkali, Standard Solutions.
7.8.1 Sodium Hydroxide Solution (0.0866 N)Dissolve 3.5
g of sodium hydroxide (NaOH) in water and dilute to 1 L.
(WarningCorrosive. Can cause severe burns or blindness.
Evolution of heat produces a violent reaction or eruption upon
too rapid mixture with water (see Annex A3.2.)). Standardize
with potassium acid phthalate and adjust to 0.0866 N as
described in Practice E 200, or alternative use.
7.8.2 Sodium Carbonate Solution (0.0725 N)Dissolve
3.84 g of Na 2CO3 in water and dilute to 1 L.
7.9 2,2,4-Trimethylpentane(isooctane),
Standard 15
(WarningExtremely flammable. Harmful if inhaled. Vapors
may cause flash fire. (See Annex A3.3.)).

the thermometers, it can be done in such a manner that the

sensing elements are at the midpoint of the thermometer bulbs.
The thermometer bulbs and temperature-sensing elements shall
not touch the bomb, bucket, or water jacket.
8.2 Calorimeter Jacket Controller and Auxiliary
EquipmentAdjust the jacket controller, valves, heater, etc., as
recommended by the calorimeter manufacturer.
9. Standardization
9.1 Energy Equivalent of the CalorimeterBenzoic acid
shall be used as the primary standard (WarningOxygen
vigorously accelerates combustion. See A3.1). Choose a
sample mass so that the temperature rise is approximately
equivalent to an energy change of 30 000 J. Initially determine
the energy equivalent by averaging six determinations made
using benzoic acid over a period of at least 3 days.
9.1.1 A relative standard deviation (RSD) of 0.1 % or less
for the six determinations must be achieved. If not, continue to
run until six determinations establish a value that has a RSD of
0.1 % or better. If this degree of precision cannot be achieved,
review the procedure, critical measurements, mechanical operations and everything that may contribute to scatter in the
results. After establishing an energy equivalent value, determine the value at frequent intervals using benzoic acid (every
1 or 2 days of testing) with the average of the last six
determinations being used for the energy equivalent as long as
the last six determinations have a RSD of 0.1 % or less.
9.1.2 If any part of the equipment is changed or any part of
the procedure is altered, redetermine the value. Make each
determination in accordance with Section 10. Determine the
correction for nitric acid (HNO3) as described in 11.3 and
substitute in the following equation:
W 5 ~Q b 3 m 1 e1!/Dt

8. Preparation of Apparatus
8.1 Arrangement of ApparatusInstall the thermometers as
recommended by the manufacturer of the calorimeter. Position
the mercury-in-glass thermometer so that the bulb is halfway to
the bottom of the bucket and locate the thermistor with its
sensing element at about the midpoint of the thermometer bulb.
Mount these elements so that exactly the same length is
immersed each time the calorimeter is used. Install a thermistor
in the water jacket with the element immersed to the same
depth as in the bucket. It is helpful, but not necessary to have
mercury-in-glass calorimetric thermometers in both the bucket
and jacket for quick temperature observations. Thermistors can
be taped to these thermometers. If the thermistors are taped to

(3)

where:
W = energy equivalent of calorimeter, J/C,
m = mass of benzoic acid, g,
Dt = corrected temperature rise, as calculated in accordance with 11.1 or 11.2, C,
e1 = correction for heat of formation of nitric acid, J, and
Qb = heat of combustion of benzoic acid, J/g calculated
from the certified value in kilojoules per gram mass
given for NBS Standard 39i. Multiply kilojoules per
gram mass by 1000 to obtain joules per gram (Note
5).
NOTE 42,2,4-trimethyl pentane may be used for checking the energy
equivalent of the system for use with volatile fuels.
NOTE 5Multiply the heat evolved by combustion of the standard
sample by the following factor.16
1 1 1026@197 ~P 2 3.04! 1 42~~m/V! 2 3!

12
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.
13
Obtainable from the National Institute of Standards and Technology, Clopper
and Quince Orchard Roads, Gaithersburg, MD 20899. as Standard Sample 39i.
14
Cellophane tape Scotch Brand No. 610, available from 3M Co., meets the
specification requirements.
15
Obtainable from the National Institute of Standards and Technology, Clopper
and Quince Roads, Gaithersburg, MD 20899, as Standard Sample No. 217b.

(4)

1 30~~Mw/ V! 2 3! 2 45~ t 2 25!#

where:
P
= initial absolute pressure of oxygen, MPa (1 atm = 0.101325
MPa) at temperature t,
m
= mass of benzoic acid, g,

16

See NBS Monograph 7, p. 12.

D 4809 00
Mw
V
t

will cover the puncture upon removal of the needle. Seal down
the flap by pressing lightly with a metal spatula. Reweigh the
cup with the tape and sample. Take care throughout the
weighing and filling operation to avoid contacting the tape or
cup with bare fingers. Place the cup in the curved electrode and
arrange the fuse wire so that the central portion of the loop
presses down on the center of the tape disk.
10.6 Bomb AssemblyAssemble the bomb and tighten the
cover securely. Connect the bomb to the oxygen cylinder and
slowly admit oxygen until a pressure of 3.0 MPa (30 atm) is
attained. Do not purge the bomb to remove entrapped air.
Disconnect the bomb from the oxygen cylinder and replace the
valve cover. (WarningA violent explosion may occur.) Be
careful not to overcharge the bomb. If by accident, the oxygen
introduced into the bomb does exceed 4.0 MPa (40 atm) DO
NOT proceed with the combustion. A violent explosion,
capable of rupturing the bomb, might occur. Detach the filling
connection and exhaust the bomb in the usual manner. Discard
the sample.

= mass of water placed in bomb before combustion, g,

= internal volume of bomb, L, and
= temperature to which the combustion reaction is referred, C
(final temperature of the calorimeter).

9.2 Heat of Combustion of Pressure-Sensitive Tape

Determine the heat of combustion of the pressure-sensitive
tape in accordance with Section 10 using about 1.2 g of tape
and omitting the sample. Make at least three determinations
and calculate the heat of combustion as follows:
Q pst 5 ~Dt 3 W 2 e 1!/a

(5)

where:
Qpst = heat of combustion of the pressure-sensitive tape,
J/g
Dt
= corrected temperature rise, as calculated in accordance with 11.1 or 11.2, C,
W
= energy equivalent of the calorimeter, J/C,
= correction for the heat of formation of HNO3, J, and
e1
a
= mass of the pressure-sensitive tape, g.
9.2.1 Average the determinations, and redetermine the heat
of combustion of the tape whenever a new roll is started.

NOTE 7Pressures within the range of from 2.5 to 3.55 MPa (25 to 35
atm) may be used, provided the same pressure is used for all tests,
including standardization.

10. Procedure
10.1 Turn on the apparatus. Make all electrical connections
and open the water lines.
10.2 Before beginning, be sure that the bomb and its fittings
are completely dry, inside and out.
10.3 Measure a piece of firing wire 100 mm long and attach
the wire to the bomb electrodes forming a U-shaped loop.
10.4 Pipet 1.0 cm3 of water into the bomb and cover with a
watch glass.
10.5 Mass of Sample:
10.5.1 Weigh the sample cup to 0.01 mg on a semimicro
analytical balance. Place a piece of pressure-sensitive type
(Note 6) across the top of the cup, trim around the edge with a
razor blade, and seal tightly. Place a 3 by 12-mm strip of tape
creased in the middle and sealed by one edge in the center of
the tape disk to give a flap arrangement. Weigh the cup and
tape. Remove from the balance with forceps. Fill a hypodermic
syringe with the sample. The volume of sample necessary to
produce a temperature rise equivalent to approximately 30 000
J can be estimated as follows:
V 5 ~W 3 0.0032!/~Q 3 D!

10.7 Calorimeter Water:

10.7.1 Adjust the temperature of the calorimeter water. The
choice of the temperature to which the water is adjusted before
weighing depends on a number of factors, including room
temperature, the desired initial temperature of the experiment,
and the relative heat capacities of the calorimeter bucket,
water, and bomb. No definite rule can be given, but the
operator will learn by experience how to select the proper
temperature under the conditions of his particular laboratory
and apparatus. The following can be used as a guide:
Isothermal method
Adiabatic method

10.7.1.1 Isoperibol MethodAdjust the temperature such

that after assembly of the calorimeter bomb and bucket its
temperature will be a few tenths of a degree below the desired
initial temperature.
10.7.1.2 Adiabatic MethodAdjust the temperature so that
the initial temperature of the determination will be as close to
some fixed values as possible. Control the mean temperature of
all determinations within more than 60.5C and the temperature rise for all determinations within 60.3C.
10.7.2 Weigh the calorimeter bucket to 60.05 g on a
heavy-duty analytical balance. After once establishing the dry
bucket weight, it need only be checked occasionally. Fill with
the desired quantity of water (2000 to 2100 g) and reweigh to
0.05 g (Note 6). The exact quantity of water is not important as
long as it is enough to cover the bomb and its fittings and is the
same in each determination.

(6)

where:
V = volume of sample to be used, cm3,
W = energy equivalent of the calorimeter, J/C,
Q = approximate heat of combustion of the sample, MJ/
kg, and
D = density, g/cm3, of the sample.
or
V 5 ~W 3 1.3!/~Q 3 D!

3.0 to 3.5C below jacket temperature

1.5 to 1.8C below room temperature

(7)

NOTE 6For relatively high-boiling samples, such as non-volatile (i.e.

IBP above 180C) kerosine-type jet fuels, it is not necessary to use tape.

NOTE 8The change in the mass of the water in the calorimeter bucket
due to evaporation after weighings will affect the energy equivalent. The
effect of this loss is small and cancels if the procedure of placing the bomb
in its bucket and completing the assembly of the system is carried out in
the same manner and in the same length of time in the calibration
experiments as in the measurement of the heat of combustion.

10.5.2 Add the sample to the cup by inserting the tip of the
needle through the tape disk at a point so that the flap of tape

10.7.3 Immediately after weighing, place the bucket in

position in the calorimeter jacket, carefully place the bomb in

where:
Q = approximate heat of combustion of the sample, Btu/lb.

D 4809 00
the bucket, and complete the firing circuit. Close the calorimeter cover and lower thermometers and thermistors.

10.9 Procedure for Adiabatic Method:

10.9.1 Start the stirrer motor and turn on the calorimeter
controller. Use the manual control switch of the controller to
bring the jacket temperature in close agreement with the bucket
temperature. Allow the controller to automatically control the
temperature and wait 15 min for equilibrium to be attained. At
this point, and at the end point also, control the temperature of
the jacket to the same temperature as the bucket, or slightly
(0.005C at most) below. Make readings at 1-min intervals
until three consecutive readings show no change. Fire the
sample by depressing the button of the ignition unit. The pilot
light should glow momentarily and the temperature should start
increasing in about 15 s. (If the temperature does not start
rising, the experiment has misfired and must be discontinued.)
Read and record the initial resistance, estimating the value to
the nearest 0.00005C.
10.9.2 After 6 min from firing, begin reading temperature
every minute. Continue until three consecutive readings show
no change, or the readings decrease. Read and record the final
temperature reading estimating the value to the nearest
0.0005C.
10.10 Analysis of Bomb Contents:
10.10.1 Turn off the controller and stirrer and remove the
bomb from the calorimeter. Open the needle valve and allow
the gas to escape at a uniform rate such as to reduce the
pressure to atmospheric in not less than 1 min. Open the bomb
and examine the interior for unburned carbon. If any trace of
unburned carbon is found, the experiment should be rejected.
Wash the interior of the bomb including the electrodes and the
sample cup with a fine jet of water and quantitatively collect
the washings in a 500-cm 3 Erlenmeyer flask. Use a minimum
amount of wash water, preferably less than 300 cm3. Titrate the
washings with standard alkali solution using methyl red
indicator.
10.10.2 Determine the sulfur content of the sample to the
nearest 0.02 % sulfur as described in Test Method D 129,
D 1266-IP 107, D 2622, D 3120, D 4294, or D 5453 depending
upon the volatility of the sample.
10.10.3 When iron or Chromel C wire is used, remove and
measure the combined pieces of unburned firing wire, and
subtract from the original length. Record the difference as wire
consumed.

NOTE 9The bomb should be lowered into the calorimeter withouttouching the water with the fingers. This can be done by using a hook on
which the bomb can be hung and which can be removed after the bomb
is in place in the calorimeter bucket. A hook made of a piece of brass rod
about 1.6 mm (116 in.) in diameter has been found satisfactory. The
hooked ends of the rod are inserted into holes on opposite sides of the
screw top of the bomb and are easily removed after the bomb is in place.
It is very important that all operations in the experimental procedure be
carried out in an identical manner throughout for the energy equivalent
and heat of combustion measurements.

10.8 Procedure for Isoperibol Method:

10.8.1 Start the stirrer motor and the controller on the jacket
heater to bring the temperature of the water in the jacket to
28C. Take time and temperature readings over a 25-min
period. During this period there are three definite time intervals:
10.8.1.1 An initial period of about 6 to 9 min during which
the temperature change results solely from thermal leakage and
heat of stirring.
10.8.1.2 A middle period of about 12 min, at the beginning
of which the charge in the bomb is fired, and during which the
temperature change is due primarily to the heat liberated by the
combustion reaction in the bomb and partly to thermal leakage
and heat of stirring, and
10.8.1.3 A final period of 9 to 11 min during which the
temperature change is again due solely to thermal leakage and
heat of stirring.
10.8.2 Allow the temperature of the calorimeter water to
drift up to the starting temperature and then make and record
readings of the time and temperature of the initial period.
During this initial period when the rate of temperature rise is
constant, make observations of temperature at 1-min intervals.
The starting temperature always has the same value as determined from the calibration runs.
10.8.3 When the firing temperature is reached, fire the
sample by closing the firing circuit through the fuse wire in the
bomb by depressing the button on the ignition unit. The pilot
light should glow momentarily and the temperature should start
increasing in about 15 s. If the circuit does not close, or if it
remains closed, or if the temperature does not start rising, the
experiment has misfired and must be discontinued. After the
combustion of the sample and during the middle period when
the temperature is rising rapidly, take temperature measurements at 30s intervals. After about 3 min, the rate of temperature rise will decrease so that temperature readings may be
taken with more accuracy. These readings shall be continued
until the rate of temperature change has been constant for at
least 10 min. The readings made after the rate of temperature
change has become constant constitute the final period.

11. Calculation
11.1 Temperature Rise Isoperibol Method Using data
obtained in Section 10, plot a graph of readings of temperature
versus time and calculate the corrected temperature rise, Dt, in
C as follows:
Dt 5 tf 2 ti 2 r 1~b 2 a! 2 r2~c 2 b!

(8)

where:
Dt = corrected temperature rise, C,
a = time of firing,
b = time (to nearest 0.1 min) when the temperature rise
reaches 63 % of total (obtained graphically or numerically),
c
= time at beginning of final period in which the rate of
temperature change with time has become constant,

NOTE 10During the initial and final periods the thermometer should
be read with the highest possible care, since the overall precision of the
determination depends directly upon these temperature measurements.
During the middle period, because of the very rapid rate of temperature
rise, it is not possible to make readings as carefully as during the initial
and final periods. This is not important because the readings of the middle
period are used only for calculating the relatively small correction for
thermal leakage and heat of stirring.

D 4809 00
TABLE 1 Values of Factor A

ti
tf
r1

= temperature at time of firing, C,

= temperature at time c, C,
= rate at which the temperature was rising during the
initial period before firing, C, and
r2 = rate at which the temperature as rising during the final
period, C.
11.2 Temperature Rise, Adiabatic Method Using data
obtained in Section 10, calculate the temperature rise,D t, in
C, as follows:
Dt 5 tf 2 t i

MJ/kg

MJ/kgC

43.00
43.25
43.50
43.75
44.00
44.25
44.50
44.75
45.00
45.25
45.50

0.00157
0.00167
0.00178
0.00188
0.00199
0.00209
0.00219
0.00230
0.00240
0.00250
0.00261

45.75
46.00
46.25
46.50
46.75
47.00
47.25
47.50
47.75
48.00

0.00271
0.00282
0.00292
0.00302
0.00313
0.00323
0.00333
0.00344
0.00354
0.00365

= gross heat of combustion at constant pressure,

MJkg, and
H
= hydrogen content, mass %
Qbtu/lb = (Q, MJ/kg)/0.002326
Qcal/g = (Q, MJ/kg)/0.0041868
11.5 Net Heat of CombustionCalculate the net heat of
combustion17 as follows:

= correction for the heat of formation of the HNO3,

J = cm3 of standard (0.0866 N) NaOH solution used
in titration 3 5,
e2 = correction for the heat of formation of sulfuric acid
(H2SO 4), J = 58.6 3 percentage of sulfur in
sample 3 mass of sample, g.
e 3 = correction for the heat of combustion of pressuresensitive tape, J = mass of tape, g 3 heat of combustion of tape J/g.
e4 = correction for heat of combustion of firing wire, MJ
= 1.13 3 millimetres of iron wire consumed/106
= 0.96 3 millimetres of Chromel C wire consumed/10 6
11.4 Gross Heat of CombustionCalculate the gross heat
of combustion by substituting in the following equations:
Qg ~gross tC! 5 ~Dt 3 W e1 e2 e3 e4!/1000 M

(10)

Qg ~gross, 25C! 5 Q g ~gross, tC! 1 A~t 25!

(11)

Dt
W
M
t
e1, e2, e3, e4
A

Qg(Gross, t C)

MJ/kgC

where:
Qgp

e1

Qg(gross, 25C)

MJ/kg

(9)

where:
Dt = corrected temperature rise, C,
tf
= final equilibrium temperature, C, and
= temperature at time of firing, C.
ti
11.3 Thermochemical Correction (Annex A2)Calculate
the following corrections for each test:

where:
Qg(gross, tC)

Qg(Gross, t C)

Qn~net, 25C! 5 Q g~Q ggross, 25C! 2 0.2122 3 H

where:
Qn(net, 25C)

= net heat of combustion at constant pressure, MJ/kg,

Qg(gross, 25C) = gross heat of combustion at constant
volume, MJ/kg, and
H
= mass percent of hydrogen in the
sample.
When the percentage of hydrogen in the sample is not
known, determine the hydrogen in accordance with Test
Methods D 1018 or D 3701.
12. Report
12.1 Net heat of combustion is the quantity required in
practical applications. Both gross and net heat are reported to
the nearest 0.002 MJ/kg.
12.1.1 To obtain the gross or net heat of combustion in cal
(I.T.)/g or Btu/lb divide by the appropriate factor given in 3.2.5
reporting to the nearest 0.5 cal/g or 1 Btu/lb.

= gross heat of combustion at constant

volume and final temperature of the
experiment, expressed as MJ/kg,
= gross heat of combustion at constant
volume expressed as MJ/kg,
= corrected temperature rise, C,
= energy equivalent of calorimeter, J/C
= mass of sample, g,
= final temperature of combustion, C,
= corrections as described in 11.3, and
= correction factor, MJ/kg C to correct
from final temperature of combustion
to 25C 15 where values of factor A are
given in Table 1.

13. Precision and Bias 18

13.1 PrecisionThe precision of this test method as determined by the statistical examination of interlaboratory test
results is as follows.
13.1.1 RepeatabilityThe difference between successive
results obtained by the same operator with the same apparatus
under constant operating conditions on identical test material
17

See NBS Monograph 7, p. 16.

The precision and bias values in this statement were determined in a
cooperative laboratory program that follows RR: D02 1007. Supporting data have
been filed at ASTM Headquarters and may be obtained by requesting
RR: D02 1229.
18

NOTE 11The gross heat of combustion at constant pressure may be

calculated as follows:
Qgp 5 Q g 1 0.006145H

(13)

(12)

D 4809 00
would, in the long run, in the normal and correct operation of
the test method, exceed the following values only in one case
in twenty.

Reproducibility, MJ/kg
Gross
Net
Method
1. All fuels
2. Nonvolatile
3. Volatile

Repeatability, MJ/kg
Method
1. All fuels
2. Nonvolatile
3. Volatile

Gross

Net

0.097
0.096
0.100

0.096
0.099
0.091

0.228
0.239
0.207

0.324
0.234
0.450

13.2 BiasThe bias of the procedure in this test method as

determined by the statistical examination of interlaboratory test
results is as follows:

13.1.2 ReproducibilityThe difference between two single

and independent results obtained by different operators working in different laboratories on identical test material would, in
the long run, exceed the following values only in one case in
twenty.

Bias, MJ/kg
Gross
0.001

Net
0.089

ANNEXES
(Mandatory Information)
A1. APPARATUS FOR HEAT OF COMBUSTION TEST

such that the bomb will be completely immersed in water when

the calorimeter is assembled. It shall have a device for stirring
the water thoroughly and at a uniform rate but with minimum
heat input. Continuous stirring for 10 min shall not raise the
temperature more than 0.01C starting with identical temperatures in the calorimeter, room, and jacket. The immersed
portion of the stirrer shall be coupled to the outside through a
material of a low-heat conductivity.

A1.1 Test Room

A1.1.1 The room in which the calorimeter is operated must
be free from drafts and not subject to sudden temperature
changes. The exact temperature is not important as long as it is
in the range from 23 to 26C (74 to 78F) and is held constant.
The temperature must be constant, not only throughout the day,
but from one time of the year to another. The direct rays of the
sun shall not strike the calorimeter jacket, bridge, and galvanometer. Adequate facilities for lighting, heating, and ventilation should be provided. Thermostatic control of room temperature and controlled humidity are desirable.

A1.4 Jacket
A1.4.1 The calorimeter bomb, bucket, and water shall be
completely enclosed within a stirred water jacket and supported so that its sides, top, and bottom are approximately 1 cm
from the jacket walls. The jacket may be arranged so as to
remain at a constant temperature, or with provisions for
automatically adjusting the jacket temperature to equal that of
the calorimeter bomb, bucket, and water for adiabatic operation. It must be constructed so that any water evaporating from
the jacket will not condense on the calorimeter bucket.20

A1.2 Oxygen Bomb

A1.2.1 The oxygen bomb shall meet the requirements
specified in Practice E 144 and have an internal volume of 350
6 50 mL. All parts shall be constructed of materials that are
not affected by the combustion process or products sufficient to
introduce measurable heat input or alteration of end products.
If the bomb is lined with platinum or gold, all openings shall be
sealed to prevent combustion products from reaching the base
metal. The bomb must be designed so that all liquid combustion products can be completely recovered by washing the
inner surfaces. There must be no gas leakage during a test. The
bomb must be capable of withstanding a hydrostatic pressure
test to a gage pressure of 20.7 MPa (3000 psi) at room
temperature without stressing any part beyond its elastic
limit.19 If necessary, modify the bomb such that the feet are 12
mm high to allow for better water circulation under the bomb.
A1.3 Calorimeter Bucket
A1.3.1 The calorimeter bucket shall be made of metal
(preferably copper or brass) with a tarnish-resistant coating,
and with all outer surfaces highly polished. Its size shall be

A1.5 Thermometers
A1.5.1 Temperatures in the jacket and the calorimeter,
respectively, shall be measured with the following thermometers:
A1.5.1.1 Etched stem, mercury-in-glass, ASTM Bomb
Calorimeter Thermometers, having a range from 66 to 95F, 19
to 35C, 18.9 to 25.1C, or 23.9 to 30.1C as specified, and
conforming to the requirements for Thermometer 56F, 56C,
116C, or 117C, respectively, as prescribed in Specification E 1.
Each of these thermometers shall have been tested for accuracy
at intervals no larger than 2.5F or 1.5C over the entire
graduated scale. Corrections shall be calculated to 0.005F or
0.002C, respectively, for each test point.

19
The oxygen bomb, Parr No. 1108 or equivalent, available from Parr Instrument
Co., 211 Fifty-third St., Moline, IL 61265.

20
The Calorimeter Jacket, Parr No. 1261 or equivalent, available from Parr
Instrument Co., meets the specification requirements.

D 4809 00
A1.5.2 Temperature in the calorimeter shall be measured
with the following thermometers:
A1.5.2.1 Platinum resistance, thermistor, or other temperature measuring devices which when used with its associated
instrumentation will measure the temperature rise repeatably
with a recorded resolution of 0.0001C and a repeatability such
that the precision requirements for the energy equivalent are
met. Further, that these specifications are limited to the
requirements that the mean temperature of all determinations
not deviate by more than 0.05C and that the temperature rise
for all experiments be within 60.3C.

circuit to indicate when current is flowing. A step-down

transformer connected to a 115 V. 50/60-Hz lighting circuit or
storage battery may be used21 (WarningThe ignition circuit
switch shall be of themomentary contact type, normally open,
except when held closed by the operator.).

A1.6 Automatic Calorimeter Microprocessor Controller

A1.6.1 In place of manually recording temperatures and
calculating the energy equivalent, an automatic controller may
be used. It shall be capable of storing calorimeter temperature
readings taken at accurate intervals, firing the bomb and ending
the experiment. The stored information along with the sample
mass, nitric acid correction and sulfur content, when entered
into the instrument, shall be used to calculate the desired
energy equivalent or heat of combustion.

A1.9 Sample Cup

A1.8 Timing Device

A1.8.1 A watch or other timing device capable of measuring time to 1 s is required for use with the isoperibol
method.

A1.9.1 A low-form platinum cup, 26 mm in diameter and 11

mm deep with a spun rim.22 Base metal alloy crucibles are
acceptable if after a few preliminary firings the weight does not
change significantly between tests.

21
Ignition Unit, Parr No. 2901, available from Parr Instrument Co., meets the
specification requirements.
22
Sample Cup, Parr No. 43A6, available from Parr Instrument Co., has been
found satisfactory.

A1.7 Firing Circuit

A1.7.1 A 6 to 16-V alternating or direct current is required
for ignition purposes with an ammeter or pilot light in the

A2. CORRECTIONS

consequently a larger error can be tolerated. For this calculation 0.8 % S, 99.2 % CH2 was taken as the empirical composition of fuel oil. If a 0.6-g sample of such a fuel oil is burned
in a bomb containing 1 cm3 of water, the H2SO4 formed will be
approximately 0.17 N.
A2.2.2.2 Using data from National Bureau of Standards
Circular No. 500, the heat of reaction SO2(g) + 12 O2(g) + 651
H2O (1) H 2SO4 650 H2O (1) at constant volume and 3 MPa
is 301.4 kg/mole.
A2.2.3 Heat of Combustion of Fuse WireWhen using
platinum wire no correction need be applied for the heat of
combustion of the wire. The electrical energy required can be
neglected if the same length of wire is used in both the energy
equivalent and unknown experiments. When using iron or
Chromel C wire, the following heats of combustion are
accepted:

A2.1 Thermometer Corrections

A2.1.1 It is not necessary to apply stem corrections to the
thermometers.
A2.2 Thermochemical Corrections
A2.2.1 Heat of Formation of Nitric AcidA correction of 5
J is applied for each cubic centimetre of standard (0.0866 N)
NaOH solution used in the acid titration. This is based on the
assumption that (1) all of the acid titrated is HNO3 and (2) the
heat of formation of 0.1 N HNO3 under the test conditions is
57.8 kJ/mole. When H2SO4 is also present, part of the
correction for H2SO4 is contained in the e1 correction, and the
remainder in the e 2 correction.
A2.2.2 Heat of Formation of Sulfuric AcidA correction of
5.86 kJ is applied to each gram of sulfur in the sample. This is
based upon the heat of formation of 0.17 N H2SO4, which
is + 301.4 kJ/mole. But, a correction equal to 2 3 57.8 kJ/mole
of sulfur was applied for H2SO4 in the e 1 correction. Thus, the
additional correction necessary is 301.4 (2 3 57.8) = 185.8
kJ/mole or 5.86 kJ/g of sulfur.
A2.2.2.1 The value of 5.86 kJ/g of sulfur is based on a fuel
oil containing a relatively large amount of sulfur since as the
percentage of sulfur decreases, the correction decreases and

Iron wire, No. 34 B & S gage =

Chromel C wire
=

1.13 J/mm
0.96 J/mm

A2.2.4 Heat of Combustion of Pressure-Sensitive Tape

The correction for the heat of combustion of the tape (as
determined in accordance with 9.2) assumes complete combustion of the tape.

D 4809 00
A3. PRECAUTIONARY STATEMENTS

A3.1 Oxygen
Do not exceed the sample size limits.
Following manufacturers commendations for filling the
bomb.
Do not use oil or grease on regulators, gages, or control
equipment.
Use only with equipment conditioned for oxygen service by
carefully cleaning to remove oil, grease, and other combustibles.
Keep combustibles away from oxygen and eliminate ignition
sources.
Keep surfaces clean to prevent ignition or explosion, or both,
on contact with oxygen.
Always use a pressure regulator. Release regulator tension
before opening cylinder valve.
All equipment and containers used must be suitable and
recommended for oxygen service.
Never attempt to transfer oxygen from cylinder in which it is
received to any other cylinder.
Do not mix gases in cylinders.
Do not drop cylinder. Make sure cylinder is secured at all
times.
Keep cylinder valve closed when not in use.
Stand away from outlet when opening cylinder valve.
Keep cylinder out of sun and away from heat.
Keep cylinder from corrosive environment.
Do not use cylinder without label.
Do not use dented or damaged cylinders.

For technical use only. Do not use for inhalation purposes.

Use only in well-ventilated area.
See compressed gas association booklets G-4 and G-4.1 for
details of safe practice in the use of oxygen.
A3.2 Sodium Hydroxide
Before using, secure information on procedures and protective measures for safe handling.
Do not get in eyes, on skin, on clothing.
Avoid breathing dusts or mists.
Do not take internally.
When handling, use chemical safety goggles or face shield,
protective gloves, boots and clothing.
When mixing with water, add slowly to surface of solution
to avoid violent spattering. In the preparation of solutions do
not use hot water, limit temperature rise, with agitation, to
10C/min or limit solution temperature to a maximum of 90C.
No single addition should cause a concentration increase
greater than 5 %.
A3.3 2,2,4-Trimethylpentane
Keep away from heat, sparks, and open flame.
Keep container closed.
Use with adequate ventilation.
Avoid buildup of vapors and eliminate all sources of
ignition, especially nonexplosion-proof electrical apparatus
and heaters.
Avoid prolonged breathing of vapor or spray mist.
Avoid prolonged or repeated skin contact.

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