ASTM D4809-95
(Test Method)Standard Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision Method)
Standard Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision Method)
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.
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Designation: D 4809 – 95 An American National Standard
Standard Test Method for
Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb
Calorimeter (Precision Method)
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.
1. Scope D 1193 Specification for Reagent Water
D 1266 Test Method for Sulfur in Petroleum Products
1.1 This test method covers the determination of the heat of
(Lamp Method)
combustion of hydrocarbon fuels. It is designed specifically for
D 2622 Test Method for Sulfur in Petroleum Products by
use with aviation turbine fuels when the permissible difference
X-Ray Spectrometry
between duplicate determinations is of the order of 0.2 %. It
D 3120 Test Method for Trace Quantities of Sulfur in Light
can be used for a wide range of volatile and nonvolatile
Liquid Petroleum Hydrocarbons by Oxidative Microcou-
materials where slightly greater differences in precision can be
lometry
tolerated.
D 3701 Test Method for Hydrogen Content of Aviation
1.2 In order to attain this precision, strict adherence to all
Fuels by Low Resolution Nuclear Magnetic Resonance
details of the procedure is essential since the error contributed
Spectrometry
by each individual measurement that affects the precision shall
E 1 Specification for ASTM Thermometers
be kept below 0.04 %, insofar as possible.
E 144 Practice for Safe Use of Oxygen Combustion
1.3 Under normal conditions, the method is directly appli-
Bombs
cable to such fuels as gasolines, kerosines, Nos. 1 and 2 fuel
E 200 Practice for Preparation, Standardization, and Stor-
oil, Nos. 1-D and 2-D diesel fuel and Nos. 0-CT, 1-CT, and
age of Standard Solutions for Chemical Analysis
2-CT gas turbine fuels.
1.4 Through the improvement of the calorimeter controls
3. Terminology
and temperature measurements, the precision is improved over
3.1 Definitions:
that of Test Method D 240.
3.1.1 gross heat of combustion—expressed as megajoules
1.5 The values stated in SI units are to be regarded as the
per kilogram. The gross heat of combustion at constant volume
standard.
of a liquid or solid fuel containing only the elements carbon,
1.6 This standard does not purport to address the safety
hydrogen, oxygen, nitrogen, and sulfur is the quantity of heat
concerns, if any, associated with its use. It is the responsibility
liberated when a unit mass of the fuel is burned in oxygen in
of the user of this standard to establish appropriate safety and
an enclosure of constant volume, the products of combustion
health practices and determine the applicability of regulatory
being gaseous carbon dioxide, nitrogen, sulfur dioxide, and
limitations prior to use. For specific hazard statements, see 7.6,
liquid water, with the initial temperature of the fuel and the
7.8, Note 3, Note 4, Note 5 and Note 11, 10.6, Note A1.1 and
oxygen and the final temperature of the products at 25°C.
Annex A3.
Gross heat of combustion (see Note 1) is represented by the
2. Referenced Documents symbol Q .
g
2.1 ASTM Standards:
NOTE 1—Users of this test method desiring to calculate D H° for a pure
D 129 Test Method for Sulfur in Petroleum Products (Gen-
eral Bomb Method)
Annual Book of ASTM Standards, Vol 11.01.
D 240 Test Method for Heat of Combustion of Liquid
Annual Book of ASTM Standards, Vol 05.02.
Hydrocarbon Fuels by Bomb Calorimeter 5
Annual Book of ASTM Standards, Vol 14.03.
D 1018 Test Method for Hydrogen in Petroleum Fractions Annual Book of ASTM Standards, Vol 14.02.
Annual Book of ASTM Standards, Vol 15.05.
Prosen, E. J., “Experimental Thermochemistry.” F. D. Rossini, editor, Inter-
science Publishers, 1956, pp. 129–148. Reliable values for heats of combustion of
This test method is under the jurisdiction of ASTM Committee D-2 on pure compounds are given in National Bureau of Standards Circular C-461,
Petroleum Products and Lubricantsand is the direct responsibility of Subcommittee “Selected Values of Properties of Hydrocarbons” (U.S. Government Printing Office,
D02.05on Petroleum, Coke, and Carbon Materials. Washington, DC, 1947) and in F. D. Rossini, et al, “Selected Values of Physical and
Current edition approved Aug. 15, 1995. Published October 1995. Originally Thermodynamic Properties of Hydrocarbons and Related Compounds,” Carnegie
published as D 4809 – 88. Last previous edition D 4809 – 90. Press, Pittsburgh, PA, 1953. These compilations were prepared by F. D. Rossini, et
Annual Book of ASTM Standards, Vol 05.01. al, as part of American Petroleum Institute Research Project 44.
Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.
D 4809
A
Conversion factor is exact.
compound should note that corrections must be applied to the value of Q
g
for buoyancy of air, heat capacities of reaction components, reduction to
4. Summary of Test Method
a constant-pressure process, and deviations of the reaction from the
thermodynamic standard state. In any comparison of measurements on
4.1 The heat of combustion is determined by burning a
pure compounds with those cited in these compilations, the user of this
weighed sample in an oxygen-bomb calorimeter under con-
test method should realize that impurities of various kinds, including
trolled conditions. The temperature increase is measured by a
water and foreign hydrocarbons may cause significant effects on the
temperature reading instrument which allows the precision of
values obtained for particular samples of material.
the method to be met. The heat of combustion is calculated
3.1.2 net heat of combustion—expressed as megajoules per
from temperature observations before, during, and after com-
kilogram. The net heat of combustion at constant pressure of a
bustion, with proper allowance for thermochemical and heat-
liquid or a solid fuel containing only the elements carbon,
transfer corrections. Either isoperibol or adiabatic calorimeters
hydrogen, oxygen, nitrogen, and sulfur is the quantity of heat
may be used.
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 5. Significance and Use
combustion being carbon dioxide, nitrogen, sulfur dioxide, and
5.1 The heat of combustion is a measure of the energy
water, all in the gaseous state, with the initial temperature of
available from a fuel. A knowledge of this value is essential
the fuel and the oxygen and the final temperature of the
when considering the thermal efficiency of equipment for
9,10
products of combustion at 25°C. The net heat of combustion
producing either power or heat.
is represented by the symbol Q and is related to the gross heat
n 5.2 The mass heat of combustion, that is, the heat of
of combustion by the following equation:
combustion per unit mass of fuel, is measured by this proce-
Q ~net, 25°C!5 Q ~gross, 25°C!2 0.2122 3 H (1) dure. Its magnitude is particularly important to weight-limited
n g
vehicles such as airplanes, surface effect vehicles, and hydro-
where:
foils as the distance such craft can travel on a given weight of
Q (net, 25°C) = net heat of combustion at constant
n
fuel is a direct function of the fuel’s mass heat of combustion
pressure, MJ/kg,
and its density.
Q (gross, 25°C) = gross heat of combustion at constant
g
5.3 The volumetric heat of combustion, that is, the heat of
volume, MJ/kg, and
combustion per unit volume of fuel, can be calculated by
H = mass % of hydrogen in the sample.
multiplying the mass heat of combustion by the density of the
3.1.3 energy equivalent (effective heat capacity or water
fuel (mass per unit volume). The volumetric heat of combus-
equivalent)—the energy equivalent of the calorimeter ex-
tion, rather than the mass heat of combustion, is important to
pressed as joules per degree Celsius, J/°C.
volume-limited craft such as automobiles and ships, as it is
NOTE 2—The energy equivalent may be expressed in any energy unit
directly related to the distance traveled between refuelings.
and any temperature unit so long as the value is used consistently
6. Apparatus
throughout the calculations.
6.1 Test Room, Bomb, Calorimeter, Jacket, Thermometers,
3.2 Units:
and Accessories, as described in Annex A1.
3.2.1 Temperatures are measured in degrees Celsius.
6.2 Semimicro Analytical Balance, having a sensitivity of
3.2.2 Time is expressed in minutes and decimal fractions
0.01 mg as specified in 10.5.1.
thereof. It can be measured in minutes or seconds, or both.
6.3 Heavy-Duty Analytical Balance, having a sensitivity of
3.2.3 Masses are measured in grams. No buoyancy correc-
0.05 g as specified in 10.7.2.
tions are applied except to obtain the mass of benzoic acid.
3.2.4 The energy unit of measurement employed in this test
7. Reagents and Materials
method is the joule with the heat of combustion reported in
7.1 Purity of Reagents—Reagent grade chemicals shall be
megajoules per kilogram (Note 3).
used in all tests. Unless otherwise indicated, it is intended that
1 MJ/kg 5 1000 J/g (2)
all reagents shall conform to the specifications of the Commit-
NOTE 3—In SI the unit of heat of combustion has the dimension J/kg,
tee on Analytical Reagents of the American Chemical Society,
but for practical use a multiple is more convenient. The MJ/kg is 11
where such specifications are available. Other grades may be
customarily used for the representation of heats of combustion of
used, provided it is first ascertained that the reagent is of
petroleum fuels.
sufficiently high purity to permit its use without lessening the
3.2.5 The following relationships may be used for convert-
accuracy of the determination.
ing to other units:
7.2 Purity of Water—Unless otherwise indicated, references
A
1 cal (International Table calorie) = 4.1868 J
to water shall be understood to mean reagent water conforming
1 Btu (British thermal unit) = 1055.06 J
to Specification D 1193, Type IV or better.
A
1 cal (I.T.)/g = 0.0041868 MJ/kg
A
1 Btu/lb = 0.002326 MJ/kg
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Derivation of equations has been filed at ASTM Headquarters. Request RR: listed by the American Chemical Society, see Analar Standards for Laboratory
D02–1346. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
See Jessup, R. S., “Precise Measurement of Heat of Combustion with a Bomb and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
Calorimeter,” NBS Monograph 7, U.S. Government Printing Office. MD.
D 4809
7.3 Benzoic Acid —The acid must be pelleted before use. 9. Standardization
7.4 Firing Wire—0.127 mm (No. 36 gage) platinum wire,
9.1 Energy Equivalent of the Calorimeter—Benzoic acid
No. 34B&S gage iron wire or Chromel C resistance wire, cut
shall be used as the primary standard (Note 4). Choose a
in 100-mm lengths.
sample mass so that the temperature rise is approximately
7.5 Methyl Red Indicator.
equivalent to an energy change of 30 000 J. Initially determine
7.6 Oxygen—Commercial oxygen produced from liquid air
the energy equivalent by averaging six determinations made
can be used without purification (Warning—See Note 4.)
using benzoic acid over a period of at least 3 days.
Oxygen prepared by electrolysis of water cannot be used
9.1.1 A relative standard deviation (RSD) of 0.1 % or less
without purification as it can contain some hydrogen. Combus-
for the six determinations must be achieved. If not, continue to
tible impurities may be removed by passage over copper oxide
run until six determinations establish a value that has a RSD of
at 500°C.
0.1 % or better. If this degree of precision cannot be achieved,
review the procedure, critical measurements, mechanical op-
NOTE 4—Warning: Oxygen vigorously accelerates combustion. (See
A3.1.) erations and everything that may contribute to scatter in the
results. After establishing an energy equivalent value, deter-
7.7 Pressure-Sensitive Tape—Cellophane tape 38 mm (1 ⁄2
13 mine the value at frequent intervals using benzoic acid (every
in.) wide, free of chlorine and sulfur.
1 or 2 days of testing) with the average of the last six
7.8 Alkali, Standard Solutions.
determinations being used for the energy equivalent as long as
7.8.1 Sodium Hydroxide Solution (0.0866 N)—Dissolve 3.5
the last six determinations have a RSD of 0.1 % or less.
g of sodium hydroxide (NaOH) in water and dilute to 1 L.
9.1.2 If any part of the equipment is changed or any part of
(Warning—See Note 5.) Standardize with potassium acid
the procedure is altered, redetermine the value. Make each
phthalate and adjust to 0.0866 N as described in Practice E 200,
determination in accordance with Section 10. Determine the
or alternative use.
correction for nitric acid (HNO ) as described in 11.3 and
NOTE 5—Warning: Corrosive. Can cause severe burns or blindness.
substitute in the following equation:
Evolution of heat produces a violent reaction or eruption upon too rapid
W 5 ~Q 3 m 1 e !/Dt (3)
b 1
mixture with water. (See Annex A3.2.)
7.8.2 Sodium Carbonate Solution (0.0725 N)—Dissolve where:
3.84gofNa CO in water and dilute to 1 L. W = energy equivalent of calorimeter, J/°C,
2 3
m = mass of benzoic acid, g, (Note 5),
7.9 2,2,4-Trimethylpentane (isooctane), Standard.
Dt = corrected temperature rise, as calculated in accor-
NOTE 6—Warning: Extremely flammable. Harmful if inhaled. Vapors
dance with 11.1 or 11.2, °C,
may cause flash fire. (See Annex A3.3.)
e = correction for heat of formation of nitric acid, J, and
Q = heat of combustion of benzoic acid, J/g calculated
b
8. Preparation of Apparatus
from the certified value in kilojoules per gram mass
8.1 Arrangement of Apparatus—Install the thermometers as
given for NBS Standard 39i. Multiply kilojoules per
recommended by the manufacturer of the calorimeter. Position
gram mass by 1000 to obtain joules per gram (Note
the mercury-in-glass thermometer so that the bulb is halfway to
8).
the bottom of the bucket and locate the thermistor with its
NOTE 7—2,2,4-trimethyl pentane may be used for checking the energy
sensing element at about the midpoint of the thermometer bulb.
equivalent of the system for use with volatile fuels.
Mount these elements so that exactly the same length is
NOTE 8—Multiply the heat evolved by combustion of the standard
immersed each time the calorimeter is used. I
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