IP 12/79 BS 2000 : Part 12 : 1993

(2001)

Determination of specific energy

1 Scope 3.1
gross heat of combustion1
This method provides for the determination of the the gross heat of combustion of a fuel at constant
gross heat of combustion of liquid fuels, and volume is the number of heat units measured as
formulae are given for calculating the net heat of being liberated at 25 °C when unit weight of the
combustion. fuel is burned in oxygen saturated with water
vapour in a bomb under standard conditions. The
WARNING – The use of this standard may involve resultant materials in the bomb are considered as
hazardous materials, operations and equipment. This being gaseous oxygen, carbon dioxide, sulphur
standard does not purport to address all of the dioxide, nitrogen, liquid water in equilibrium with its
safety problems associated with its use. It is the vapour and saturated with carbon dioxide, other
responsibility of the user of this standard to compounds in solution, and solid ash. The gross
establish appropriate safety and health practices and heat of combustion2 is represented by the symbol
determine the applicability of regulatory limitations Qg.
prior to use.
3.2
2 Summary of method net heat of combustion1
the heat of combustion of a fuel at constant
pressure is the number of heat units measured as
2.1 A weighed quantity of the sample is burned
being liberated at 25 °C when unit weight of fuel is
in oxygen in a bomb calorimeter under controlled
burned in oxygen at constant pressure such that the
conditions. The heat of combustion is calculated
heat released is equal to the gross heat of
from the weight of the sample and the rise in
combustion of the fuel at constant pressure less the
temperature, with proper allowance for heat transfer
latent heat of evaporation at 25 °C and constant
and for the formation of nitric and sulphuric acids in
pressure of the water both originally contained in
the bomb, no account being taken of other minor
the fuel and formed by its combustion. The net heat
products formed. The value so obtained is the gross
of combustion is represented by the symbol Qn.
heat of combustion at constant volume.
3.3
2.2 The bomb calorimeter is calibrated by the
unit of measurement
combustion of benzoic acid.
the unit of measurement employed in this method is
the joule. If the results are required in terms of
2.3 Either isothermal or adiabatic calorimeter
calories per gram (calIT/g) or British Thermal units
jackets may be used.
per pound (BtuIT/lb) the following relationships may
be used:
3 Definitions
1 calIT/g = 4,1868 J/g (exactly)
For the purpose of this standard, the following 1 BtuIT/lb = 2,326 J/g (exactly)
terms and definitions apply.

1
The definitions of gross and net heat of combustion are based on BS 526 or ASTM D2382, Sec. 3, 'Definitions of the
Calorific Value of Fuel'.
2
Users of this method desiring to calculate )H°k298 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. See, for example, E. J. Prosen, 'Experimental
Thermochemistry', F. D. Rossini, editor, Interscience Publishers, 1956, pp. 129-148. 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' (US 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. In any comparison of measurements on pure compounds with those cited in these compilations, the user of this
method should realise that impurities of various kinds, including water and foreign hydrocarbons, may cause significant
effects on the values obtained from particular samples of material.

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 SPECIFIC ENERGY OF LIQUID FUELS, IP 12

4 Apparatus 4.6.1 Thermometer reading eyepiece, magnifying

type with adjustable focus, for use with
4.1 The room in which the calorimeter mercury-in-glass thermometers.
equipment is located shall be free from draughts and
sudden changes in temperature. 4.7 Oxygen charging equipment, conforming to
the specification given in Annex A4.
4.2 Calorimeter bomb, conforming to the
specification given in Annex A1. 5 Materials and reagents

4.3 Calorimeter vessel, metal vessel polished on 5.1 Water, unless otherwise indicated,
the outside, preferably at least 75 mm higher than references to water shall be understood to mean
the bomb, preferably of such cross-sectional area distilled or demineralised reagent water.
that 2 litres of water just covers the bomb.
5.2 Oxygen, under pressure in cylinders, free
4.3.1 Stirrer, a mechanical device for stirring the from combustible material.
water in the calorimeter vessel at a uniform rate.
The stirring shall be thorough, but not so rapid as to 5.3 Ignition wire, 0,1±0,03 mm dia. platinum
cause appreciable heating of the water. Continuous wire. The same diameter and length of wire should
stirring of the water in the calorimeter vessel of the be used in the calibration and determination.
isothermal jacketed apparatus for 10 min after
thermal equilibrium has been established shall not 5.4 Firing cotton (if required), a strand of wick
cause an increase in temperature of more than as specified for use with ASTM D1266—IP 107,
0,01°C. With the adiabatic jacketed apparatus dried at 100 to 105 °C and stored over silica gel
continuous stirring of the water in the calorimeter until required. The heat of combustion of each batch
vessel for 10 min after thermal equilibrium has been of firing cotton must be determined.
established shall not cause an increase in
temperature of more than 0,002 °C. The portion of 5.5 Sodium hydroxide solution, approx. 0,1 N,
the stirrer immersed in the calorimeter vessel shall accurately standardized.
be connected to the outside portion with material of
low heat conductivity. 5.6 Benzoic acid, powder or pellet form, of
thermochemical standard of purity and of a heat of
4.3.2 Water jacket, a double walled metal vessel combustion certified by the National Physical
containing water, fitted with a lid and leaving an air Laboratory or the National Bureau of Standards.
gap of preferably 10 mm all around the calorimetric Powdered material shall be compressed into pellets.
vessel.
5.7 Cellulose adhesive tape, plain transparent
4.3.2.1 The isothermal jacket shall be arranged so cellulose film of width not less than 25 mm and
as to remain at a uniform temperature (maximum thickness 0,05 to 0,075 mm. Use only
variation 0,05 °C) during the test. cellulose-based film. The heat of combustion of
each batch of tape must be determined.
4.3.2.2 Adiabatic calorimeters shall be capable of
circulating water continuously through both jacket 5.8 Indicator, the following alternatives may be
and lid. The system shall be fitted with heating and used:
cooling devices such that the temperature of the
jacket water is rapidly adjusted to that of the water 5.8.1 Methyl purple solution, aqueous solution
in the calorimeter vessel with a sensitivity containing approximately 0,1% active constituent,
sufficiently good to satisfy the requirements of or
9.5.2.
5.8.2 Methyl red solution, 60% alcohol-aqueous
4.4 Fuel cup, a range of fuel cups that may be solution containing approximately 0,1% indicator.
used is illustrated in Annex A2.
6 Safety precautions
4.5 Ignition system, conforming to the
specifications given in Annex A5. 6.1 The weight of sample shall be such that the
heat developed during the combustion shall in no
4.6 Thermometers, conforming to the case exceed 90 J/ml bomb capacity; and the total
specifications given in Annex A3. weight of sample, together with any combustible

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 SPECIFIC ENERGY OF LIQUID FUELS, IP 12

material such as cellulose tape, shall be calculated nearest 0,1 mg to find the weight of benzoic acid.
in advance, so that the given limit is not exceeded. Pipette 1 ml of water into the bomb (to saturate the
oxygen used for combustion with water vapour).
6.2 Provision must be made to ensure that the Place the fuel cup in the circular ring support
oxygen filling pressure does not exceed the safety attached to the terminals of the bomb.
limit (see Annex A4 concerning oxygen charging
equipment). 8.1.1.1 Attach a measured length of ignition wire
(approx. 100 mm, see Section 5.3) across the bomb
The operator shall not go near the calorimeter until terminals so as to form a U-shape loop and arranged
at least 20 sec have elapsed from the time of firing. so that the central portion of the loop is in contact
with the benzoic acid; or
6.3 The bomb must be completely submerged in
water during firing and the charge must not be 8.1.1.2 Attach a measured length of ignition wire
ignited if there is any evidence of gas leakage. Also, (approx. 100 mm, see Section 5.3) across the bomb
do not fire the bomb if it has been accidentally terminals under light tension. Weigh a suitable
over-charged with oxygen to a pressure greater than length of dry firing cotton and tie it at the centre of
40 bar (39,5 atm, 580 lb/in2). the ignition wire. Insert the free end of the firing
cotton into the crucible so that it is in contact with
6.4 Because of the risk of explosion, it is the benzoic acid.
strongly recommended that the firing point and the
oxygen cylinder be situated outside the room or 8.1.2 Close the bomb securely.
safety enclosure containing the calorimeter, but in
any case firing shall be by remote control in order to 8.1.3 Admit oxygen slowly to a gauge pressure of
minimize the risk of injury to the operator (see 30 bar (29,6 atm, 430 psig).
Annex A5 concerning Ignition Systems).
8.1.4 Determine the effective heat capacity of the
7 Sample bomb by making not less than 5 combustions of the
certified benzoic acid using the standard quantity of
7.1 Take samples of liquid fuels of flash point water. The standard quantity of water is such that
less than 38 °C directly into a container of not less the cover of the bomb (but not terminals) is
than 200 ml capacity, fill the container as immersed and the effective heat capacity of the
completely as possible and close immediately after system is approx. 10 500 joules/°C. If necessary,
taking the sample. Store samples in a refrigerator at make preliminary combustions of benzoic acid to
below 4 °C until required. The fuel shall be establish the correct weight of water. Once
transferred to the fuel cup at a temperature as near established this shall be the standard quantity of
as possible to the storage temperature. water, weighed to within 0,5 g, to be used in all
subsequent determinations.
7.2 If results are required on a dry basis,
determine the water content independently and 8.1.5 When using isothermal apparatus follow the
correct the result accordingly. details of procedure described in 9.4 and 9.6. When
using adiabatic apparatus follow the details of
8 Standardisation procedure described in 9.5 and 9.6. Calculate the
effective heat capacity as described in 10.1 to 10.4.
8.1 Determination of effective heat capacity,
energy equivalent or water equivalent, using 9 Procedure
tweezers, place in the weighed fuel cup (Type 2 or
3 of Annex A2 Fig. 4) the approximate weight of For liquid fuels of flash point below 38 °C proceed
benzoic acid derived from the relation: as in 9.1.1 or 9.1.2 and continue the determination
as in 9.4, 9.6, and 9.7 when using isothermal
m = 90 x Bomb capacity to ml apparatus or as in 9.5, 9.6, and 9.7 when using
26 500 adiabatic apparatus. For liquid fuels of flash point
above 38 °C proceed as in 9.2.1 or 9.2.2 and
where m is the approx. weight of benzoic acid, in g. continue the determination as in 9.4, 9.6, and 9.7
when using isothermal apparatus or as in 9.5, 9.6,
8.1.1 Weigh the fuel cup and its contents to the and 9.7 when using adiabatic apparatus.

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Figure 1: Sealed fuel cup assemblies

9.1 Liquid fuels of flash point less than 38 °C the nearest 0,1 mg. Charge the fuel cup by lifting
the lip of the sealing tape and introducing the
9.1.1 Fuel cup type 1 or 4 Annex A2 Fig. 4, weigh required weight [Note 1] of liquid fuel with a
the fuel cup to 0,1 mg. Cover the cup with the hypodermic syringe. Replace the tape to seal the
cellulose adhesive tape, trim around the edge with fuel cup, allow the temperature to reach equilibrium
a razor blade, and seal tightly. Puncture the tape (Section 7.1) and weigh the fuel cup and its
with a large needle to make an opening somewhat contents to the nearest 0,1 mg. Pipette 1 ml of
larger than the diameter of the hypodermic syringe water into the bomb. Place the fuel cup in the
needle. Place a 4 x 12 mm strip of tape, creased in circular ring support attached to the terminals of the
the middle and sealed along one side, in the centre bomb. Attach a measured length of ignition wire
of the tape disk to give a flap arrangement which (see Section 5.3) across the bomb terminals under
will cover the hole when finally sealed down, as light tension. Tie the free end of the firing cotton to
shown in Fig. 1, Type 4. Weigh the cup and tape, the centre of the ignition wire and with a pin make
and remove from the balance with forceps. Add the about six small holes in the tape sealing the mouth
required weight [Note 1] of sample with a of the fuel cup. Immediately close the bomb
hypodermic syringe through the hole in the tape. securely.
Seal the flap down over the hole by pressing lightly
with a metal spatula. Allow the temperature to 9.2 Liquid fuels of flash point greater than 38°C
reach equilibrium (7.1) and reweigh the cup, tape, [Note 2]
and sample. Care must be taken throughout the
weighing and filling operation to avoid contacting 9.2.1 Fuel cup type 2, 3, or 4 of Annex A2 Fig. 4,
the tape or cup with bare fingers. Place the cup in place the required weight [Note 1] of liquid fuel in
the curved electrode and attach a measured length the weighed fuel cup. Weigh the fuel cup and its
of ignition wire (see 3.3) across the bomb terminals contents to the nearest 0,1 mg. Pipette 1 ml of
such that the central portion of the loop presses water into the bomb. Place the fuel cup in the
down on the centre of the tape disk. Pipette 1 ml of circular ring support attached to the terminals of the
water into the bomb and immediately close the bomb. Attach a length of ignition wire across the
bomb securely: or, alternatively bomb terminals under light tension. Weigh a suitable
length of dry firing cotton and tie it at the centre of
9.1.2 Fuel cup type 1 or 4 of Annex A2 Fig. 4, the ignition wire. Dip the free end of the firing
weigh the fuel cup to the nearest 0,1 mg. Cover the cotton into the contents of the fuel cup and
fuel cup top with two pieces of cellulose adhesive immediately close the bomb securely; or,
tape, such that they slightly overlap as shown in alternatively
Fig. 1, Type 1. Fix one end of a weighed length of
firing cotton into the overlap, the other end being 9.2.2 Fuel cup type 2, 3, or 4 of Annex A2 Fig. 4,
free for attachment to the ignition wire. Weigh the place the required weight [Note 1] of sample in the
fuel cup and the attached tape and firing cotton to weighed fuel cup. Weigh the cup and sample to

12.4
 SPECIFIC ENERGY OF LIQUID FUELS, IP 12

0,1 mg. Place the cup in the curved electrode and 9.4.3 At the end of the sixth minute fire the
arrange the fuse wire so that the central portion of charge by closing the firing circuit for not longer
the loop just dips into the contents of the cup. than 2 sec. CAUTION: see 6.2.
Pipette 1 ml of water into the bomb. Immediately
close the bomb securely. DO NOT GO NEAR THE BOMB UNTIL AT LEAST 20 SECONDS
HAVE ELAPSED FROM THE TIME OF FIRING
NOTE 1 - The weight of the sample shall be controlled
such that: 9.4.4 Record the temperatures at 45, 60, 75, 90,
and 105 sec after the time of firing. By interpolation
M = 90 x Bomb capacity in ml between these readings the time at which the
Qg temperature rise reached 60% of its final value will
later be found [Note 5].
where
M is the required weight of sample in g; 9.4.5 After the rapid rise period (about 4 to 5 min)
Qg is approx. heat of combustion of the record the temperature at 1 min intervals on each
sample in J/g. completed min after the time of firing. Continue
these readings until the difference between
NOTE 2 - Liquid luck having flash point in the range 38 to
successive readings has been constant for 5 min
60 °C may tend to lose a small proportion of their more
volatile components on exposure to the atmosphere.
[Note 5]. From this series determine the time at the
Weigh the sample into the fuel cup and seal immediately beginning of the period in which the rate of
in the bomb whilst avoiding exposure to draughts. temperature change with time is constant.
Determine also the rate of change of temperature
9.3 Admit oxygen slowly to a gauge pressure of with time.
30 bar (29,6 atm, 430 psig).
9.4.6 The temperature rise shall be between
9.4 Isothermal jacket calorimeters 2,5 and 3,5 °C and the final temperature shall not
be more than 1 °C (and preferably not more than
Fill the water jacket with water at a temperature 0,5 °C) above that of the jacket.
within 3 °C of room temperature and ensure that it
remains constant throughout. Fill the calorimeter NOTE 3 - Temperatures should be read to 0,001 °C. This
vessel with the standard quantity of water (see will not be possible during the rapid period, and the most
accurate readings which are practicable at this time
8.1.4) weighed to within 0,5 g. The initial
should be recorded. Mercury-in-glass thermometers shall
temperature of the bomb and calorimeter shall be: be tapped lightly before reading, particularly when the
temperature is falling, to prevent errors caused by sticking
(i) in the range 15 to 32 °C; of the mercury. A convenient method of effecting this is
(ii) above the dew point; to mount a small buzzer directly on top of the
(iii) approx. 2,5 °C below the temperature of thermometer. and operate it for a few moments before
the water jacket and preferably within 2 °C each reading. Use an eyepiece to facilitate thermometer
of the temperature of standardisation (see reading.
Note 9).
NOTE 4 - The rate of temperature Change with time shall
be considered constant if the variation in the rate does
9.4.1 Place the prepared bomb, CAUTION: see
not exceed 0,001 °C/min. the rate of change of
Section 6, in the calorimeter vessel, check that
temperature shall be calculated as the mean of the
there is no leakage of oxygen, confirm that the firing relevant recordings.
leads are dead, and make the appropriate electrical
connexions. Put the covers in position, arrange the NOTE 5 - When the approx. heat of combustion of the
thermometer and stirrer so that they do not touch fuel is known to within 1 500 joule/g, the expected
the bomb or vessel, and start the stirrer. temperature rise may be determined from the relation:

9.4.2 When the temperature is rising steadily and MQg

at least 5 min after starting the stirrer, record a t=
W
series of temperature readings [Note 3] at 1 min
intervals for 5 min, from which the temperature at where
the end of the sixth minute, i.e. time of firing, will Qg is the approx. gloss heat of combustion,
later be found by extrapolation. The rate of in J/g,
temperature rise in the 5 min period before firing M is the weight of sample in g, and
shall be constant [Note 4]. W is the effective heat capacity of
calorimeter in J/°C.

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 SPECIFIC ENERGY OF LIQUID FUELS, IP 12

Calculate the temperature at the 60% point by the bomb and release the pressure uniformly at such
adding to the temperature at the time of firing, 60% a rate that the operation takes at least 1 min. Open
of the expected temperature rise. Start an additional the bomb and examine the inside for traces of
stopwatch at the time of the first reading of the unburned oil or soot; if either is found discard the
series of temperature recordings made before firing. determination [Note 7].
Stop the stopwatch when the calculated 60%
temperature rise is attained and record the time. 9.6.1 Rinse out the interior of the bomb, including
the fuel cup, with a fine jet of distilled water, and
9.5 Adiabatic calorimeters collect the washings, which shall not exceed a
volume of 350 ml, in a beaker. Add a few drops of
Fill the calorimeter vessel with the standard quantity indicator and titrate with the sodium hydroxide
of water, weighed to within 0,5 g (see 8.1.4), the solution to determine the quantity of nitric and
temperature of which shall be within the range of sulphuric acids formed in the combustion.
15 to 32 °C, shall be above the dew point and
preferably within 2 °C of the temperature of NOTE 6 - If a constant temperature is not obtained within
standardisation (see Note 9). Ensure that the jacket 15 min of firing the apparatus should be considered
is filled with water at a temperature close to, and suspect.
preferably equal to or slightly below, that of the
calorimeter vessel. Place the prepared bomb in the NOTE 7 - The combustion of highly leaded fuels may
cause appreciable corrosion inside a stainless steel bomb,
calorimeter vessel, check that there is no leakage of
but this is not to be taken as a reason for rejecting the
oxygen, confirm that the firing leads are dead and test result.
make the appropriate electrical connexions. Place
the covers in position, arrange the stirrer, 9.7 When the sulphur content of the sample is
thermometer, and temperature regulating device in unknown, filter the neutralised washings through a
position so that they do not touch the bomb or medium texture filter paper such as a Whatman No.
calorimeter walls. Switch on the calorimeter stirrer, 40, and determine the sulphur content as prescribed
jacket stirrer, heaters, and cooling coil and run the in ASTM D129–IP 61.
apparatus for 5 min to attain equilibrium.

9.5.1 If, at the start, the bomb is markedly

10 Calculation and report
different in temperature from the calorimeter vessel,
10.1 Correct all temperatures for thermometer
more than 5 min may be required to reach
errors according to the certificate.
equilibrium.
10.2 Temperature rise in isothermal jacket
9.5.2 Check that the apparatus is at equilibrium by
calorimeter
recording the temperature to the nearest 0,001 °C
[Note 3] at 1 min intervals. Successive readings
Using data obtained as prescribed in Section 9.4,
shall not differ by more than 0,001 °C and shall not
compute the temperature rise, )t, in an isothermal
show any progressive tendency. When four
jacket calorimeter as follows:
successive readings have complied with the
requirements consider the apparatus to be at
)t = tc – ta – r1 (b – a) – r2 (c – b)
equilibrium and record the temperature to the
nearest 0,001 °C as the firing temperature (ta, see
where
10.3). Fire the charge by closing the firing circuit for
)t is the corrected temperature rise, in
not longer than 2 sec. CAUTION: see 6.2.
°C;
DO NOT GO NEAR THE BOMB UNTIL AT LEAST 20 SECONDS a is the time for firing, in min;
HAVE ELAPSED FROM THE TIME OF FIRING b is the time (to nearest 0,1 min)
when the temperature rise reaches
9.5.3 Record the temperature to the nearest 60% of the total, in min;
0,001 °C at 1 min intervals until the same c is the time at beginning of period in
temperature is recorded for three successive which the rate of temperature
readings. Record this value as the final temperature change with time has become
tf (see 10.3) [Note 6]. constant (after combustion), in min;
ta is the temperature at time of firing,
9.6 Fifteen minutes after the ignition, remove in °C;
the bomb from the calorimeter, dry the outside of tc is the temperature at time, c, in °C;

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 SPECIFIC ENERGY OF LIQUID FUELS, IP 12

r1 is the rate at which the temperature NOTE 9 - The term DT is an approximation which is
was rising during the 6 min period applied to adjust the effective heat capacity of the system
before firing, in °C/min; at the mean temperature, T, of the determination to the
r2 is the rate at which the temperature reference temperature of 25 °C, and is only necessary
when the mean temperature of the bomb standardisation
was rising during the 5 mm period
and the determination differ by more than 3 °C. It is
after time c in °C min. If the calculated as follows:
temperature was falling, r2 is
negative and the quantity [– r2(c – ⎛ MB ⎞
b)] is positive. DT = α M w − β ⎜ M s + ⎟ J / deg C
⎝ 4 ⎠
10.3 Temperature rise in adiabatic jacket
where
calorimeter Mw is the weight of water in the system, in
kg;
Using data obtained as prescribed in 9.5 and 10.1, Ms is the weight of stainless steel in the
compute the temperature rise, )t in an adiabatic system, in kg;
jacket calorimeter as follows: MB is the weight of bronze and brass in the
system, in kg.
)t = tf – ta
The values " and $ are obtained from the graph in Fig.2.
The mean temperature T in °C is given by the relation
where
)t is the corrected temperature rise, in
Ta + t f
°C; t=
ta is the temperature at time of firing, 2
in °C;
tf is the final maximum recorded where
temperature, in °C. ta is the temperature at the time of firing
in °C;
tf is the final maximum recorded
10.4 Effective heat capacity of the calorimeter temperature in °C.

Calculate the effective heat capacity of the Plot the calculated values of DT in J/°C against values of
calorimeter, W in joules/°C as follows: T between 15 and 35 °C.

[QB + 12
. (25 − t f )]m + e1 + e2 10.5 Gross heat of combustion
W= − DT
Δt
[Notes 8 and 9] Calculate the gross heat of combustion at constant
volume and at 25 °C, in J/g from the equation:
where
QB is the certified calorific value of the Δ t × (W + DT ) − e1 − e2 − e3 − e4
Qg =
benzoic acid in J/g (see 5.6); M
m is the weight of benzoic acid, in g;
)t is the corrected temperature rise, where
°C; W is the effective heat capacity of the
e1 is the correction for the heat of system at 25 °C, in J/°C;
formation of acids in DT is the correction at the mean
J (1 ml 0,1 N NaOH = 5,9 J); temperature, T, obtained from the
e2 is the correction for heat of data plotted as described in Note 9,
combustion of firing cotton in J (if in J/°C (apply this correction in
used) (heat of combustion of batch whole numbers);
x weight of cotton); )t is the corrected temperature rise, in
DT is the correction for test °C;
temperature variation [see Note 9] e1 is the correction for the heat of
in J/°C. (Apply this correction in formation of acids, in joules (1 ml
whole numbers.) 0,1 N NaOH = 5,9 J);
e2 is the correction for firing cotton (if
NOTE 8 - The term [QB +1,2(25 – tf)] relates the certified used) in joules (heat of combustion
heat of combustion of benzoic acid at 25 °C to the final of batch x weight of cotton used);
temperature of the calorimeter.

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 SPECIFIC ENERGY OF LIQUID FUELS, IP 12

Figure 2: Values of " and $ for calculating DT.

e3 is the supplementary correction for where

the sulphur content of the sample, H is the hydrogen content of the
in joules (58,6 x %S x M of sample, sample, in percent weight.
in g);
e4 is the correction for cellulose tape, The following equation may be used for the
if used, in joules (heat of calculation of net heat of combustion of aviation
combustion of hatch x M of tape gasoline and turbine fuel when the hydrogen content
used); of the sample is not known:
M is the weight of sample, in g.
Qn = 10 023 + 0,7195Qg [Note 10].
10.6 Net heat of combustion
NOTE 10 - This equation is only recommended if the
Calculate the net heat of combustion (Qn) in joules/g percentage of hydrogen is not known. It is based on the
from the following equation: previous equation and an empirical relationship between
Qn and the percentage of hydrogen in aviation gasoline
and turbine fuels, developed from data by R. S. Jessup
Qn = Qg - 212,19H
and C. S. Gragoe, 'Heat of Combustion of AN-F-28
Aviation Gasoline', National Advisory Committee of

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 SPECIFIC ENERGY OF LIQUID FUELS, IP 12

Aeronautics, Tech. Note 996, June 1945, and J. A. considered suspect if they differ by more than:
Cogliano and R. S. Jessup, 'Relationship between Net
Heat of Combustion and Aniline Gravity Product of 276 J/g (119 BtuIT/lb, 66 calIT/g)
Aircraft Fuels', National Bureau of Standards Report
2348, March 1953.
11.2 Reproducibility
10.7 To obtain the gross or net heat of
The results submitted by each of two laboratories
combustion in calIT/g or BtuIT/lb divide Qg or Qn by
should not be considered suspect unless the two
the appropriate factor given in Section 3.
results differ by more than:
10.8 Report the result as the Gross or Net Heat of
773 J/g (332 BtuIT/lb, 185 calIT/g)
Combustion to the nearest 20 J/g, or to the nearest
10 BtuIT/lb or to the nearest 5 calIT/g.
11.2.1 The precision estimates have been derived
by statistical analysis of inter-laboratory test
11 Precision results and were first published in 1971.

The following criteria should be used for judging the 11.2.2 In the light of a cooperative programme
acceptability of results (95% confidence). carried out by the ASTM/IP, it is apparent that this
method should be carried out by experienced
11.1 Repeatability operators. Under these circumstances a greatly
improved precision can be expected.
Duplicate results by the same operator should be

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 SPECIFIC ENERGY OF LIQUID FUELS, IP 12

ANNEX A

APPARATUS FOR DETERMINATION OF THE HEAT OF COMBUSTION

OF LIQUID FUELS

A1 IP Standard bomb specification Elongation at break not less than 30%.

conforming to BS 4791: 1972 lzod impact value not less than 68 Nm.

Table 1: Dimensions of bomb body, cap and closure

A1.1 General
ring
This specification covers the essential constructional
Detail Symbol Requirement
features and materials, and testing of bombs to be (see
used for determining the heat of combustion of Fig. 3)
liquid fuels, or their sulphur content, in accordance Body
with IP standard methods. External diameter to be uniform within
0,03 mm
Internal diameter D shall be not less than
A1.2 General design 55 mm
Capacity of the 325±25 ml
The proportions of the bomb shall conform to Fig. 3. combustion chamber
Thickness of side wall t not less than 0,10 D
Thickness of base T not less than 0,165 D
It shall have an internal diameter of not less than Internal radius E not less than t
55 mm and a capacity of 325±25 ml. The weight
Closure ring
of the bomb shall not exceed 3,25 kg. It shall be so Dimensions of closure
constructed that it does not leak, and can be easily ring when made of
drained. All parts enclosing the gas space shall be aluminium bronze:
Thickness of wall A not less than 0,14 D
constructed of materials which are not affected
Thickness of flange B not less than 0,17 D
sufficiently by the combustion process or products
Screw thread
to introduce measurable heat input or alteration of Nominal pitch thread ISO metric threads 1,5
the end products. The electrodes shall be made of form, and fit mm or 2 mm pitch
heat and corrosion resistant material, e.g. platinum shall be used with a
or its alloys, suitable steels or nickel chrome, and so 6H/6g (medium) fit
complying with BS
placed that when the oil cup is in position its base 3643.
shall be not less than 90 mm from the underside of ISO inch (unified)
the bomb lid. The closure of the bomb shall be so threads complying with
designed that in normal operation the bomb can be BS 1580 Unified
Threads, are
sealed and opened by hand without the use of tools acceptable during the
of any type. The calorimeter bomb seal shall be so period of change to
designed that after hand-tightening an increase of metrication.
pressure in the bomb will tighten the seal and In this case a 16 tpi
2A/2B (medium) fit
prevent leakage. shall be used.
The roots shall be
A1.3 Materials rediused: they shall not
encroach upon the
minimum wall
The bomb cap and body shall be machined from thickness.
solid or hollow forgings or bar. They shall not be Length of engagement C not less than 0,25 D
fabricated from components welded or brazed Cap
together. Thickness of cap F not less than 0,10 D
flange not less than 0,25 D
Total thickness of cap
For a bomb designed to the minimum dimensions
Crucible position
and dimensional ratios given in Table 1, the material
related to cap
shall have the following mechanical properties: Base of crucible to not less than 90 mm
underside of cap
Tensile strength not less than 550 MN/m2. Total of mass shall not exceed 3,25
Yield stress not less than 210 MN/m2. kg

12.10
 SPECIFIC ENERGY OF LIQUID FUELS, IP 12

Figure 3: Typical bomb for heat of combustion (for values of labelled dimensions see Table 1)

The material from which the bomb cap and body are For a bomb designed to the minimum dimensions
made shall, in addition, be certified to have passed and dimensional ratios given in Table 1, the material
a suitable test for resistance to intercrystalline shall have the following mechanical properties:
corrosion. If steel is used it shall be subject to the
ring test and 90° bend test, described in BS 1501-6 Tensile strength not less than 525 MN/m2.
and BS 970. Elongation at break not less than 25%.

The appropriate British Standards for suitable Aluminium bronze to BS 2872 Grade CA 103 and
materials are listed below: BS 2874 Grade CA 103 have been proved by
experience to be suitable.
BS 1501-6 Steels for use in the chemical,
petroleum, and allied industries. The appropriate British Standards are listed below:
BS 970 Wrought steels in the form of bars,
billets and forgings, up to 152,5 BS 2872: 1969 Copper and copper alloys.
mm ruling section, for automobile Forging stock and forgings.
and general engineering purposes. BS 2874: 1969 Copper and copper alloys.
BS 1503-845 Grade B for Ti for forgings. Rods and sections (other
BS 1506-845 For bars. than forging stock).

The 'closure ring' shall be made of material capable A1.4 Finish

of withstanding the pressures generated by the
combustion process and chosen to minimise galling The surface of all pressure parts shall have a
or seizing of the thread engaging the bomb body. It smooth machined or ground finish throughout. No
shall be machined from solid or hollow forgings or stamping or engraving shall be allowed except in the
bar. It shall not be fabricated from components positions indicated in Fig.3, but this restriction does
welded or brazed together. not apply to the use of electric pencils. If a knurled
surface is provided, the metal thickness shall be
increased locally by at least the depth of knurling.

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 SPECIFIC ENERGY OF LIQUID FUELS, IP 12

A1.5 Pressure test in accordance with BS 4791 W is the 34,3 S2 newtons,

S is the OD of the gasket or sealing
After completion, each bomb shall be tested under ring in mm.
a water pressure of 300 bar, which shall be
maintained in the bomb for a period of 10 min A2 Fuel cups
without leakage. After removal of the test pressure,
the external diameter of the bomb body shall not A2.1 The fuel cups illustrated in Fig. 4 are suitable
show an increase exceeding 0.1% of the diameter for use in this method.
measured, and the threads shall be examined for
galling. The performance of the bomb under this test A3 Thermometers
shall be attested by certificate.
A3.1 Temperatures in the jacket and in the
NOTE 11 - The British Standards Institution, Maylands
calorimeter, respectively, shall be measured with
Avenue, Hemel Hempstead, Herts, is prepared to accept
bombs for compliance with the pressure test. thermometers conforming to any of the following
types:
A1.6 Marking
A3.1.1 Mercury-in-glass, bomb calorimeter thermo-
A1.6.1 Each bomb body, lid, and closure ring shall meters, having a 6 °C range conforming to the
be indelibly marked with: requirements for thermometers in BS 791 or those
given in ASTM Specification El for the ASTM 116C
(a) a reference (e.g. BS 1506-845B) identifying and ASTM 117C thermometers. Each of these
the material used in its construction; thermometers shall have been tested for accuracy at
(b) the manufacturer's serial number. intervals of 0,5°C or less over the entire graduated
scale. Corrections shall be reported to 0,002°C or
A1.6.2 Each bomb assembly shall be indelibly better for each test point.
marked with test pressure to which it was
subjected; and the date on which the pressure test A3.1.2 Platinum resistance, quartz crystal or
was made. thermistor thermometers, with elements enclosed in
a metal sheath and connected to suitable electrical
A1.7 Certificates measuring equipment may be used in this method
provided the temperature measuring system meets
The manufacturer or supplier of the bomb shall or exceeds the following minimum requirements:
supply to the purchaser a copy of the steelmaker's
certificate for the steel from which the bomb has Readability, the last digit must be
been made, and also a certificate that the bomb has readable to 0,001 °C
been made wholly in accordance with this
specification. with the following information: Repeatability, in temperature rise
measurements over the same
A1.7.1 The reference number of the BS steel used 3 °C range ±0,001°C
in the construction of the bomb.
Absolute accuracy, the error in any
A1.7.2 The maker's serial number, and the date of single temperature reading shall not
manufacture of the bomb. exceed ±0,150°C

A1.7.3 The name of the testing body, the test A4 Oxygen charging equipment
pressure to which the bomb was subjected, and the
date on which the pressure test was made. A4.1 The valves, gauges, filling tube and fittings
used in the oxygen charging system must meet
A1.7.4 A certificate to the effect that a prototype industry safety codes and must be rated for use at
closure ring made of material corresponding to that input pressures up to 206 bar (3 000 psig) and
used in the manufacture of production closure rings discharge pressures up to 55 bar (800 psig).
has withstood a total load (W) as defined below, Separate gauges should be provided to show the
applied in such a way as to simulate operating supply pressure and the bomb pressure. The bomb
conditions without undergoing a permanent change gauge should be not less than 75 mm in diameter
of shape at any point greater than 0,05 mm, where: and preferably graduated from 0 to 55 bar (atm) in

12.12
 SPECIFIC ENERGY OF LIQUID FUELS, IP 12

Figure 4: Fuel cups

1 bar (atm) sub-divisions. Both gauges must be from a stepdown transformer connected to an
absolutely oil-free and must never be tested in a alternating current line or from a storage battery.
hydraulic system containing oil. The charging The firing voltage must not exceed 24 volts and
equipment should include either a pressure reducing should be held to the lowest practicable level
valve which will limit the discharge pressure to a recommended by the manufacturer. An ammeter or
maximum of 40 bar (600 psig) or a relief valve set a pilot light may be used in the circuit to indicate
to discharge at 40 bar (600 psig) in case the bomb where current is flowing, and the circuit must be
should accidentally be overcharged. Means should controlled by a double-pole, momentary contact
also be provided for releasing the residual pressure switch which remains normally open, except when
in the filling tube after the bomb valve has been held closed by the operator.
closed.
The switch shall be held in the closed position for
A5 Ignition system not more than 2 sec.

A5.1 The ignition current should be drawn either

12.13