ASTM D4809-00(2005)
(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.
1.6This 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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Standards Content (Sample)
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An American National Standard
Designation:D4809–00 (Reapproved 2005)
Standard Test Method for
Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb
Calorimeter (Precision Method)
This standard is issued under the fixed designation D4809; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber 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 D129 Test Method for Sulfur in Petroleum Products (Gen-
eral Bomb Method)
1.1 This test method covers the determination of the heat of
D240 Test Method for Heat of Combustion of Liquid
combustionofhydrocarbonfuels.Itisdesignedspecificallyfor
Hydrocarbon Fuels by Bomb Calorimeter
use with aviation turbine fuels when the permissible difference
D1018 Test Method for Hydrogen in Petroleum Fractions
between duplicate determinations is of the order of 0.2%. It
D1193 Specification for Reagent Water
can be used for a wide range of volatile and nonvolatile
D1266 Test Method for Sulfur in Petroleum Products
materials where slightly greater differences in precision can be
(Lamp Method)
tolerated.
D2622 Test Method for Sulfur in Petroleum Products by
1.2 In order to attain this precision, strict adherence to all
Wavelength Dispersive X-Ray Fluorescence Spectrometry
details of the procedure is essential since the error contributed
D3120 Test Method forTrace Quantities of Sulfur in Light
by each individual measurement that affects the precision shall
Liquid Petroleum Hydrocarbons by Oxidative Microcou-
be kept below 0.04%, insofar as possible.
lometry
1.3 Under normal conditions, the method is directly appli-
D3701 Test Method for Hydrogen Content of Aviation
cable to such fuels as gasolines, kerosines, Nos. 1 and 2 fuel
Fuels by Low Resolution Nuclear Magnetic Resonance
oil, Nos. 1-D and 2-D diesel fuel and Nos. 0-GT, 1-GT, and
Spectrometry
2-GT gas turbine fuels.
D4294 Test Method for Sulfur in Petroleum and Petroleum
1.4 Through the improvement of the calorimeter controls
Products by Energy Dispersive X-ray Fluorescence Spec-
and temperature measurements, the precision is improved over
troscopy
that of Test Method D240.
D5453 Test Method for Determination of Total Sulfur in
1.5 The values stated in SI units are to be regarded as the
Light Hydrocarbons, Motor Fuels and Oils by Ultraviolet
standard.
Fluorescence
1.6 This standard does not purport to address the safety
E1 Specification for ASTM Thermometers
concerns, if any, associated with its use. It is the responsibility
E144 Practice for Safe Use of Oxygen Combustion Bombs
of the user of this standard to establish appropriate safety and
E200 Practice for Preparation, Standardization, and Stor-
health practices and determine the applicability of regulatory
age of Standard and Reagent Solutions for Chemical
limitations prior to use. For specific hazard statements, see
Analysis
Section 7, 10.6, A1.7.1 and Annex A3.
3. Terminology
2. Referenced Documents
3.1 Definitions:
2.1 ASTM Standards:
3.1.1 gross heat of combustion—expressed as megajoules
perkilogram.Thegrossheatofcombustionatconstantvolume
This test method is under the jurisdiction of ASTM Committee D02 on
of a liquid or solid fuel containing only the elements carbon,
PetroleumProductsandLubricantsandisthedirectresponsibilityofSubcommittee
hydrogen, oxygen, nitrogen, and sulfur is the quantity of heat
D02.05 on Property of Fuels, Petroleum Coke, and Carbon Materials.
liberated when a unit mass of the fuel is burned in oxygen in
Current edition approved May 1, 2005. Published May 2005. Originally
an enclosure of constant volume, the products of combustion
approved in 1988. Last previous edition approved in 2000 as D4809–00.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
being gaseous carbon dioxide, nitrogen, sulfur dioxide, and
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
liquid water, with the initial temperature of the fuel and the
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D4809–00 (2005)
1MJ/kg 51000J/g (2)
oxygen and the final temperature of the products at 25°C.
Gross heat of combustion (see Note 1) is represented by the
NOTE 3—In SI the unit of heat of combustion has the dimension J/kg,
symbol Q .
g but for practical use a multiple is more convenient. The MJ/kg is
customarily used for the representation of heats of combustion of
NOTE 1—Usersofthistestmethoddesiringtocalculate D H°forapure
petroleum fuels.
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
3.2.5 The following relationships may be used for convert-
a constant-pressure process, and deviations of the reaction from the
ing to other units:
thermodynamic standard state. In any comparison of measurements on
A
3 1 cal (International Table calorie) = 4.1868 J
pure compounds with those cited in these compilations , the user of this
1 Btu (British thermal unit) = 1055.06 J
test method should realize that impurities of various kinds, including
A
1 cal (I.T.)/g = 0.0041868 MJ/kg
water and foreign hydrocarbons may cause significant effects on the A
1 Btu/lb = 0.002326 MJ/kg
values obtained for particular samples of material.
A
Conversion factor is exact.
3.1.2 net heat of combustion—expressed as megajoules per
kilogram.The net heat of combustion at constant pressure of a
4. Summary of Test Method
liquid or a solid fuel containing only the elements carbon,
4.1 The heat of combustion is determined by burning a
hydrogen, oxygen, nitrogen, and sulfur is the quantity of heat
weighed sample in an oxygen-bomb calorimeter under con-
liberated when a unit mass of the fuel is burned in oxygen at a
trolled conditions. The temperature increase is measured by a
constant pressure of 0.101 MPa (1 atm), the products of
temperature reading instrument which allows the precision of
combustionbeingcarbondioxide,nitrogen,sulfurdioxide,and
the method to be met. The heat of combustion is calculated
water, all in the gaseous state, with the initial temperature of
from temperature observations before, during, and after com-
the fuel and the oxygen and the final temperature of the
bustion, with proper allowance for thermochemical and heat-
4,5
productsofcombustionat25°C.Thenetheatofcombustion
transfer corrections. Either isoperibol or adiabatic calorimeters
isrepresentedbythesymbol Q andisrelatedtothegrossheat
n
may be used.
of combustion by the following equation:
Q ~net,25°C!5 Q ~gross,25°C!20.2122 3 H (1)
n g
5. Significance and Use
where:
5.1 The heat of combustion is a measure of the energy
Q (net,25°C) = net heat of combustion at constant
n available from a fuel. A knowledge of this value is essential
pressure, MJ/kg,
when considering the thermal efficiency of equipment for
Q (gross,25°C) = gross heat of combustion at constant
g
producing either power or heat.
volume, MJ/kg, and
5.2 The mass heat of combustion, that is, the heat of
H = mass % of hydrogen in the sample.
combustion per unit mass of fuel, is measured by this proce-
3.1.3 energy equivalent (effective heat capacity or water
dure. Its magnitude is particularly important to weight-limited
equivalent)—the energy equivalent of the calorimeter ex-
vehicles such as airplanes, surface effect vehicles, and hydro-
pressed as joules per degree Celsius, J/°C.
foils as the distance such craft can travel on a given weight of
fuel is a direct function of the fuel’s mass heat of combustion
NOTE 2—The energy equivalent may be expressed in any energy unit
and any temperature unit so long as the value is used consistently
and its density.
throughout the calculations.
5.3 The volumetric heat of combustion, that is, the heat of
3.2 Units: combustion per unit volume of fuel, can be calculated by
multiplying the mass heat of combustion by the density of the
3.2.1 Temperatures are measured in degrees Celsius.
3.2.2 Time is expressed in minutes and decimal fractions fuel (mass per unit volume). The volumetric heat of combus-
tion, rather than the mass heat of combustion, is important to
thereof. It can be measured in minutes or seconds, or both.
3.2.3 Masses are measured in grams. No buoyancy correc- volume-limited craft such as automobiles and ships, as it is
directly related to the distance traveled between refuelings.
tions 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 6. Apparatus
megajoules per kilogram (Note 3).
6.1 Test Room, Bomb, Calorimeter, Jacket, Thermometers,
and Accessories, as described in Annex A1.
6.2 Semimicro Analytical Balance, having a sensitivity of
Prosen, E. J., “Experimental Thermochemistry.” F. D. Rossini, editor, Inter-
0.01 mg as specified in 10.5.1.
science Publishers, 1956, pp. 129–148. Reliable values for heats of combustion of
6.3 Heavy-Duty Analytical Balance, having a sensitivity of
pure compounds are given in National Bureau of Standards Circular C-461,
0.05 g as specified in 10.7.2.
“SelectedValuesofPropertiesofHydrocarbons”(U.S.GovernmentPrintingOffice,
Washington,DC,1947)andinF.D.Rossini,etal,“SelectedValuesofPhysicaland
Thermodynamic Properties of Hydrocarbons and Related Compounds,” Carnegie
7. Reagents and Materials
Press, Pittsburgh, PA, 1953. These compilations were prepared by F. D. Rossini, et
al, as part of American Petroleum Institute Research Project 44.
7.1 Purity of Reagents—Reagent grade chemicals shall be
Derivation of equations has been filed at ASTM Headquarters. Request RR:
used in all tests. Unless otherwise indicated, it is intended that
D02–1346.
all reagents shall conform to the specifications of the Commit-
See Jessup, R. S., “Precise Measurement of Heat of Combustion with a Bomb
Calorimeter,” NBS Monograph 7, U.S. Government Printing Office. tee onAnalytical Reagents of theAmerican Chemical Society,
D4809–00 (2005)
where such specifications are available. Other grades may be Mount these elements so that exactly the same length is
used, provided it is first ascertained that the reagent is of immersedeachtimethecalorimeterisused.Installathermistor
sufficiently high purity to permit its use without lessening the in the water jacket with the element immersed to the same
accuracy of the determination. depth as in the bucket. It is helpful, but not necessary to have
7.2 Purity of Water—Unlessotherwiseindicated,references mercury-in-glass calorimetric thermometers in both the bucket
towatershallbeunderstoodtomeanreagentwaterconforming andjacketforquicktemperatureobservations.Thermistorscan
to Specification D1193, Type IV or better. be taped to these thermometers. If the thermistors are taped to
7.3 Benzoic Acid —The acid must be pelleted before use. the thermometers, it can be done in such a manner that the
7.4 Firing Wire—0.127 mm (No. 36 gage) platinum wire, sensingelementsareatthemidpointofthethermometerbulbs.
No.34B&SgageironwireorChromelCresistancewire,cut Thethermometerbulbsandtemperature-sensingelementsshall
in 100-mm lengths. not touch the bomb, bucket, or water jacket.
7.5 Methyl Red Indicator. 8.2 Calorimeter Jacket Controller and Auxiliary
7.6 Oxygen—Commercial oxygen produced from liquid air Equipment—Adjustthejacketcontroller,valves,heater,etc.,as
can be used without purification (Warning—Oxygen vigor- recommended by the calorimeter manufacturer.
ously accelerates combustion. (See A3.1.)). Oxygen prepared
9. Standardization
by electrolysis of water cannot be used without purification as
it can contain some hydrogen. Combustible impurities may be
9.1 Energy Equivalent of the Calorimeter—Benzoic acid
removed by passage over copper oxide at 500°C.
shall be used as the primary standard (Warning—Oxygen
7.7 Pressure-Sensitive Tape—Cellophane tape 38 mm (1 ⁄2
vigorously accelerates combustion. See A3.1). Choose a
in.) wide, free of chlorine and sulfur.
sample mass so that the temperature rise is approximately
7.8 Alkali, Standard Solutions.
equivalent to an energy change of 30000 J. Initially determine
7.8.1 SodiumHydroxideSolution (0.0866N)—Dissolve3.5
the energy equivalent by averaging six determinations made
g of sodium hydroxide (NaOH) in water and dilute to 1 L.
using benzoic acid over a period of at least 3 days.
(Warning—Corrosive. Can cause severe burns or blindness.
9.1.1 A relative standard deviation (RSD) of 0.1% or less
Evolution of heat produces a violent reaction or eruption upon
forthesixdeterminationsmustbeachieved.Ifnot,continueto
too rapid mixture with water (see Annex A3.2.)). Standardize
rununtilsixdeterminationsestablishavaluethathasaRSDof
with potassium acid phthalate and adjust to 0.0866 N as
0.1% or better. If this degree of precision cannot be achieved,
described in Practice E200, or alternative use.
review the procedure, critical measurements, mechanical op-
7.8.2 Sodium Carbonate Solution (0.0725 N)—Dissolve
erations and everything that may contribute to scatter in the
3.84gofNa CO in water and dilute to 1 L.
results. After establishing an energy equivalent value, deter-
2 3
7.9 2,2,4-Trimethylpentane—(isooctane), Standard mine the value at frequent intervals using benzoic acid (every
(Warning—Extremely flammable. Harmful if inhaled. Vapors
1 or 2 days of testing) with the average of the last six
may cause flash fire. (See Annex A3.3.)). determinations being used for the energy equivalent as long as
the last six determinations have a RSD of 0.1% or less.
8. Preparation of Apparatus
9.1.2 If any part of the equipment is changed or any part of
8.1 Arrangement of Apparatus—Installthethermometersas the procedure is altered, redetermine the value. Make each
recommended by the manufacturer of the calorimeter. Position determination in accordance with Section 10. Determine the
themercury-in-glassthermometersothatthebulbishalfwayto correction for nitric acid (HNO ) as described in 11.3 and
the bottom of the bucket and locate the thermistor with its substitute in the following equation:
sensingelementataboutthemidpointofthethermometerbulb.
W 5 ~Q 3 m 1 e !/Dt (3)
b 1
where:
W = energy equivalent of calorimeter, J/°C,
Reagent Chemicals, American Chemical Society Specifications, American
m = mass of benzoic acid, g,
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Ch
...
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