ASTM D240-02(2007)
(Test Method)Standard Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb Calorimeter
Standard Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb Calorimeter
SIGNIFICANCE AND USE
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.
The heat of combustion as determined by this test method is designated as one of the chemical and physical requirements of both commercial and military turbine fuels and aviation gasolines.
The mass heat of combustion, the heat of combustion per unit mass of fuel, is a critical property of fuels intended for use in weight-limited craft such as airplanes, surface effect vehicles, and hydrofoils. The range of such craft between refueling is a direct function of the heat of combustion and density of the fuel.
SCOPE
1.1 This test method covers the determination of the heat of combustion of liquid hydrocarbon fuels ranging in volatility from that of light distillates to that of residual fuels.
1.2 Under normal conditions, this test 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.
1.3 This test method is not as repeatable and not as reproducible as Test Method D 4809.
1.4 The values stated in SI units are to be regarded as the standard.
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. For specific hazard statements, see Sections 7 and 9 and A1.10 and Annex A3.
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Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation:D240–02 (Reapproved 2007)
Standard Test Method for
Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb
Calorimeter
This standard is issued under the fixed designation D240; 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 (´) 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 Liquid Petroleum Hydrocarbons by Oxidative Microcou-
lometry
1.1 This test method covers the determination of the heat of
D3701 Test Method for Hydrogen Content of Aviation
combustion of liquid hydrocarbon fuels ranging in volatility
TurbineFuelsbyLowResolutionNuclearMagneticReso-
from that of light distillates to that of residual fuels.
nance Spectrometry
1.2 Under normal conditions, this test method is directly
D4294 Test Method for Sulfur in Petroleum and Petroleum
applicable to such fuels as gasolines, kerosines, Nos. 1 and 2
Products by Energy Dispersive X-ray Fluorescence Spec-
fuel oil, Nos. 1-D and 2-D diesel fuel and Nos. 0-GT, 1-GT,
trometry
and 2-GT gas turbine fuels.
D4809 Test Method for Heat of Combustion of Liquid
1.3 This test method is not as repeatable and not as
Hydrocarbon Fuels by Bomb Calorimeter (Precision
reproducible as Test Method D4809.
Method)
1.4 The values stated in SI units are to be regarded as the
D5453 Test Method for Determination of Total Sulfur in
standard.
Light Hydrocarbons, Spark Ignition Engine Fuel, Diesel
1.5 This standard does not purport to address all of the
Engine Fuel, and Engine Oil by Ultraviolet Fluorescence
safety concerns, if any, associated with its use. It is the
E1 Specification forASTM Liquid-in-GlassThermometers
responsibility of the user of this standard to establish appro-
E200 Practice for Preparation, Standardization, and Stor-
priate safety and health practices and determine the applica-
age of Standard and Reagent Solutions for Chemical
bility of regulatory limitations prior to use. For specific hazard
Analysis
statements, see Sections 7 and 9 and A1.10 and Annex A3.
3. Terminology
2. Referenced Documents
3.1 Definitions:
2.1 ASTM Standards:
3.1.1 grossheatofcombustion,Qg(MJ/kg)—thequantityof
D129 Test Method for Sulfur in Petroleum Products (Gen-
energyreleasedwhenaunitmassoffuelisburnedinaconstant
eral Bomb Method)
volume enclosure, with the products being gaseous, other than
D1018 Test Method for Hydrogen In Petroleum Fractions
water that is condensed to the liquid state.
D1266 Test Method for Sulfur in Petroleum Products
3.1.1.1 Discussion—The fuel can be either liquid or solid,
(Lamp Method)
and contain only the elements carbon, hydrogen, nitrogen, and
D2622 Test Method for Sulfur in Petroleum Products by
sulfur. The products of combustion, in oxygen, are gaseous
Wavelength Dispersive X-ray Fluorescence Spectrometry
carbon dioxide, nitrogen oxides, sulfur dioxide, and liquid
D3120 Test Method forTrace Quantities of Sulfur in Light
water. In this procedure, 25°C is the initial temperature of the
fuel and the oxygen, and the final temperature of the products
of combustion.
This test method is under the jurisdiction of ASTM Committee D02 on
3.1.2 net heat of combustion, Qn (MJ/kg)—the quantity of
PetroleumProductsandLubricantsandisthedirectresponsibilityofSubcommittee
energy released when a unit mass of fuel is burned at constant
D02.05 on Properties of Fuels, Petroleum Coke and Carbon Material.
pressure, with all of the products, including water, being
Current edition approved May 1, 2007. Published June 2007. Originally
approved in 1957. Last previous edition approved in 2002 as D240–02.
gaseous.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
3.1.2.1 Discussion—The fuel can be either liquid or solid,
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
and contain only the elements carbon, hydrogen, oxygen,
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. nitrogen, and sulfur. The products of combustion, in oxygen,
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D240–02 (2007)
are carbon dioxide, nitrogen oxides, sulfur dioxide, and water, 5. Significance and Use
allinthegaseousstate.Inthisprocedure,thecombustiontakes
5.1 The heat of combustion is a measure of the energy
place at a constant pressure of 0.1012 MPa (1 atm), and 25°C
available from a fuel. A knowledge of this value is essential
is the initial temperature of the fuel and the oxygen, and the
when considering the thermal efficiency of equipment for
final temperature of the products of combustion.
producing either power or heat.
3.1.3 The following relationships may be used for convert-
5.2 The heat of combustion as determined by this test
ing to other units (conversion factor is exact only for Btu):
method is designated as one of the chemical and physical
1 cal (International Table calorie) = 4.1868 J
requirementsofbothcommercialandmilitaryturbinefuelsand
1 Btu (British thermal unit) = 1055.06 J and refer to as factor not exact
aviation gasolines.
1 cal (I.T.)/g = 0.0041868 MJ/kg
1 Btu/lb = 0.002326 MJ/kg 5.3 The mass heat of combustion, the heat of combustion
perunitmassoffuel,isacriticalpropertyoffuelsintendedfor
3.2 Definitions of Terms Specific to This Standard:
use in weight-limited craft such as airplanes, surface effect
3.2.1 energy equivalent—(effective heat capacity or water
vehicles, and hydrofoils. The range of such craft between
equivalent)ofthecalorimeteristheenergyrequiredtoraisethe
refueling is a direct function of the heat of combustion and
temperature 1° expressed as MJ/°C.
density of the fuel.
1MJ/kg 51000J/g (1)
InSI,theunitofheatofcombustionhasthedimensionJ/kg,
6. Apparatus
but for practical use a multiple is more convenient.The MJ/kg
6.1 Test Room, Bomb, Calorimeter, Jacket, Thermometers,
is customarily used for the representation of heats of combus-
and Accessories, as described in Annex A1.
tion of petroleum fuels.
NOTE 1—Theenergyunitofmeasurementemployedinthistestmethod
7. Reagents
is the joule with the heat of combustion reported in megajoules per
7.1 BenzoicAcid,Standard —Benzoicacidpowdermustbe
kilogram.
compressed into a tablet or pellet before weighing. Benzoic
3.3 Symbols:
acid pellets for which the heat of combustion has been
3.3.1 The net heat of combustion is represented by the
determined by comparison with the National Bureau of Stan-
symbolQ andisrelatedtothegrossheatofcombustionbythe
n
dards sample are obtainable commercially for those laborato-
following equation:
ries not equipped to pellet benzoic acid.
Q ~net,25°C!5Q ~gross,25°C!20.2122 3H (2) 7.2 Gelatin Capsules.
n g
7.3 Methyl Orange or Methyl Red Indicator.
where:
7.4 Mineral Oil.
Q (net, 25°C) = net heat of combustion at constant
n
7.5 Oxygen—Commerical oxygen produced from liquid air
pressure, MJ/kg,
can be used without purification. If purification is necessary,
Q (gross, 25°C) = gross heat of combustion at constant
g
seeA1.11(Warning—Oxygenvigorouslyacceleratescombus-
volume, MJ/kg, and
tion. See A3.2.).
H = mass% of hydrogen in the sample.
7.6 Pressure-Sensitive Tape—Cellophane tape 38 mm (1 ⁄2
in.) wide, free of chlorine and sulfur.
4. Summary of Test Method
7.7 Alkali, Standard Solution:
4.1 Heatofcombustionisdeterminedinthistestmethodby
7.7.1 Sodium Hydroxide Solution (0.0866 mol/L)—
burning a weighed sample in an oxygen bomb calorimeter
Dissolve 3.5 g of sodium hydroxide (NaOH) in water and
under controlled conditions. The heat of combustion is com-
dilute to 1 L. Standardize with potassium acid phthalate and
puted from temperature observations before, during, and after
adjust to 0.0866 mol/L as described in Practice E 200
combustion, with proper allowance for thermochemical and
(Warning—Corrosive. Can cause severe burns or blindness.
heat transfer corrections. Either isothermal or adiabatic calo-
Evolution of heat produces a violent reaction or eruption upon
rimeter jackets can be used.
too rapid mixture with water. See Annex A3.1.)
4.1.1 Temperatures can be measured in degrees Celsius.
7.7.2 Sodium Carbonate Solution (0.03625 mol/L)—
4.1.1.1 Temperatures can be recorded in either degrees
Dissolve 3.84 g of Na CO in water and dilute to 1 L.
2 3
Fahrenheit or ohms or other units when using electric ther-
Standardize with potassium acid phthalate and adjust to
mometers. Use the same units in all calculations, including
0.03625 mol/L as described in Practice E200.
standardization.
7.8 2,2,4-Trimethylpentane (isooctane), Standard —
4.1.2 Time is expressed in calculations in minutes and
(Warning—Extremely flammable. Harmful if inhaled. Vapors
decimal fractions thereof. It may be measured in minutes and
may cause flash fire. See Annex A3.3.)
seconds.
4.1.3 Masses are measured in grams and no buoyancy
corrections are applied.
Available from National Institute of Standards and Technology (NIST), 100
Bureau Dr., Stop 1070, Gaithersburg, MD 20899-1070, http://www.nist.gov as
standard sample No. 39.
3 5
Derivation of equations have been filed at ASTM Headquarters. Request Obtainable from the National Institute of Standards Technology as standard
Research Report RR: D02-1346. sample No. 217b.
D240–02 (2007)
8. Standardization Average the determinations, and redetermine the heat of
combustionofthetapeorgelatincapsule/mineraloilwhenever
8.1 Determine the Energy Equivalent of the Calorimeter—
6 a new roll or batch is started.
Average not less than six tests using standard benzoic acid.
These tests should be spaced over a period of not less than
9. Procedure
three days. Use not less than 0.9 g nor more than 1.1gof
standardbenzoicacid(C H COOH).Makeeachdetermination
9.1 Weight of Sample—Control the weight of sample (in-
6 6
accordingtotheproceduredescribedinSection9andcompute
cluding any auxiliary fuel) so that the temperature rise pro-
the corrected temperature rise, t, as described in 10.1 or 10.2.
duced by its combustion will be equal to that of 0.9 to 1.1gof
Determine the corrections for nitric acid (HNO ) and firing
benzoicacid(Note2).Weighthesampletothenearest0.1mg.
wire as described in 10.3 and substitute in the following
NOTE 2—If the approximate heat of combustion of the sample is
equation:
known, the required weight can be estimated as follows:
W 5 ~Q 3g 1e 1e !/t (3)
1 2
g 526.454/Q (5)
s
where:
where:
W = energy equivalent of calorimeter, MJ/°C,
g = mass of sample, g, and
Q = heat of combustion of standard benzoic acid, MJ/g,
Q = MJ/kg.
s
calculated from the certified value,
Some fuels contain water and particulate matter (ash) that
g = weight of standard benzoic acid sample, g,
will degrade calorimetric values. If the heat of combustion is
t = corrected temperature rise, as calculated in 10.1 or
required on a clean fuel, filter the sample to remove free water
10.2,°C,
and insoluble ash before testing.
e = correction for heat of formation of nitric acid, MJ,
9.1.1 For highly volatile fluids, reduce loss with use of tape
and
or gelatin capsule mineral oil.
e = correction for heat of combustion of firing wire, MJ.
NOTE 3—Acceptable procedures for handling volatile liquids include
8.1.1 Repeat the standardization tests after changing any those described in the reports referenced at the end of this test method.
References (1-6) describe glass sample holders: (7) describes a metal
part of the calorimeter and occasionally as a check on both
sample holder: (8) describes a gelatin sample holder.
calorimeter and operating technique.
8.2 Checking the Calorimeter for Use with Volatile Fuels—
9.1.2 Tape—Place a piece of pressure-sensitive tape across
Use 2,2,4-trimethylpentane to determine whether the results
thetopofthecup,trimaroundtheedgewitharazorblade,and
obtained agree with the certified value (47.788 MJ/kg, weight
seal tightly. Place 3 by 12-mm strip of tape creased in the
in air) within the repeatability of the test method. If results do
middle and sealed by one edge in the center of the tape disk to
not come within this range, the technique of handling the
giveaflaparrangement.Weighthecupandtape.Removefrom
sample may have to be changed (Annex A1.8). If this is not
the balance with forceps. Fill a hypodermic syringe with the
possibleordoesnotcorrecttheerror,runaseriesoftestsusing
sample. The volume of sample can be estimated as follows:
2,2,4-trimethylpentane to establish the energy equivalent for
V 5 W 30.00032 / Q 3D (6)
~ ! ~ !
use with volatile fuels.
8.3 Heat of Combustion of Pressure-Sensitive Tape or
where:
Gelatin/Mineral Oil—Determine the heat of combustion of
V = volume of sample to be used, mL,
either the pressure-sensitive tape or 0.5 g gelatin capsule/
W = energy equivalent of calorimeter, J/°C,
mineral oil in accordance with Section 9 using about 1.2 g of Q = approximateheatofcombustionofthesample,MJ/kg,
tape or 0.5 g gelatin capsule/mineral oil and omitting the and
D = density, kg/m , of the sample.
sample. Make at least three determinations and calculate the
heat of combustion as follows: 9.1.2.1 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
Q 5 ~Dt 3W 2e !/1000a (4)
pst 1
willcoverthepunctureuponremovaloftheneedle.Sealdown
where: the flap by pressing lightly with a metal spatula. Reweigh the
Q = heat of combustion of the pressure-sensitive tape or
cup with the tape and sample. Take care throughout the
pst
mineral oil, MJ/kg,
weighing and filling operation to avoid contacting the tape or
Dt = corrected temperature rise, as calculated in accor-
cupwithbarefingers.Placethecupinthecurvedelectrodeand
dance with 10.1 or 10.2,°C,
arrange the fuse wire so that the central portion of the loop
W = energy equivalent of the calorimeter, MJ/°C,
presses down on the center of the tape disk.
e = correction for the heat of formation of HNO , MJ,
1 3
9.1.3 Gelatin/Mineral Oil—Weigh the cup and gelatin cap-
and
sule.Thecapsuleshouldonlybehandledwithforceps.Addthe
a = mass of the pressure-sensitive tape or gelatin
sample to the capsule. Reweigh the cup with capsule and
capsule/mineral oil, g.
sample. If poor combustion is expected with the capsule, add
severaldropsofmineraloilonthecapsuleandreweighthecup
andcontents.Placethecupinthecurvedelectrodeandarrange
thefusewiresothatthecentralportionoftheloopcontactsthe
See Jessup, R. S., “Precise Measurement of Heat of Combustion with a Bomb
Calorimeter,” NBS Monograph 7, U. S. Government Printing Office. capsule and oil.
...
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