DIGITAL BOMB CALORIMETER

INSTRUCTION MANUAL

Manufactured by:

Toshniwal Technologies Pvt. Ltd.

B-48, Phase I
Mayapuri Industrial Area,
NewDelhi-110064 India
Tel : 011-45612992,28114425
fax ; 011-45612993
e mail : factory@toshniwaldelhi.com

TOSHNIWAL BOMB CALORIMETER WITH DIGITAL DIFFERENTIAL

TEMPERATURE / FIRING UNIT
1. INTRODUCTION
A Bomb Calorimeter measures the amount of heat generated when matter is
burnt in a sealed chamber ( Bomb) in an atmosphere of pure Oxygen gas.
Toshniwal Bomb Calorimeter provides a simple inexpensive yet accurate
method for the determination of heat of combustion, Calorific Value and the
Sulphur contents of solid & liquid fuels. The outfit provided is complete for
the analysis as per methods recommended by the Indian Standard Institute
( IS : 1359 1959), British Standard Institute ( BS 1016: Part 5:1967) and
the Institute of Petroleum ( IP 12/63T). Each part of the outfit has been
finished and tested according to the specifications laid down by these
Institutions.
2. PRINCIPLE OF OPERATION:
A known amount of the sample is burnt in a sealed chamber ( Bomb). The air
is replaced by pure Oxygen. Sample is ignited electrically. As the sample is
burnt, heat is produced. The rise in temperature is measured. Since barring
the loss of heat, the amount of heat produced by burning the sample must be
equal to the amount of heat absorbed by the calorimeter assembly. A
knowledge of the water equivalent of the calorimeter assembly and of the
rise in temperature enables to calculate the heat of combustion of the
sample.
If W= Water Equivalent of the calorimeter assembly in calories per degree
centigrade,
T= Rise in temperature in degree centigrade,
H = Heat of combustion of material in calories per gram, &
M = Mass of the sample burnt in grams,
Then WT = HM & H = WT / M

3. DEFINITIONS AND UNITS:

Calorimetric measurements involve the use of various temperature and
energy units. In order to avoid errors and confusion in the interpretation of
these data, their relationships should be well understood.
TEMPERATURE: May be measured in either Fahrenheit or centigrade
degrees. A temperature change of 1oC corresponds to a change of 1.8oF
TIME : It is customarily measured in minutes & seconds.
MASS : It is expressed in grams
HEAT ENERGY: May be expressed either as calories ( cal) or British Thermal
Units ( Btu). Calorie is the basic unit in this system and equals to 4.1868
absolute Joules and is defined as the heat energy required to raise the
temperature of one gram of water by one degree centigrade at 15.56 oC.The
British Thermal Unit equals to 251.996 cal. or 1055.07 absolute Joules and is
roughly equivalent to the heat energy required to raise the temperature of
one pound of water by one degree F at 60 oF.
HEAT OF COMBUSTION ( also thermal value, heating value or calorific
value) as determined with an Oxygen Bomb Calorimeter is defined as the
number of heat units liberated by a unit mass of the substance when burnt in
a sealed chamber of constant volume in an atmosphere of pure Oxygen gas, In
this reaction the substance and the Oxygen are initially at the same
temperature and the products of the combustion are cooled to within a few
degrees of the initial temperature. Also the water vapours formed by the
combustion are condensed to the liquid state. Therefore, a more exact
definition would specify the temperature at which the reaction begins and
ends. However the change in the specific heat of water with the possible
variations in the initial temperature is so small that this specification is not
necessary.
It is commonly expressed either in calories / gram or Btu/lb. One Cal/g = 1.8
Btu/lb.

4. CHARACTERISTIC REQUIREMENTS:
1. BOMB : When the sample burns, the pressure of gases increases rapidly.
The Bomb walls, lids & joints should be strong enough to withstand the
maximum working pressures and there should be no leaks. Normal working
pressures are about 30 atmospheres and overload pressures peak up to
100 atmospheres.
2. The capacity of Bomb should be large enough to store enough Oxygen to
ensure complete burning of the sample.
3. During burning the Nitrogen & Sulphur contents are oxidised to gases and
then to nitric acid and sulphuric acid. The Bomb must therefore be
resistant to acidic or basic ash and should be corrosion proof.
4. The stirrer unit should not generate excess amount of heat due to
stirring. Further motor heat should not reach the calorimeter, otherwise
the calculations will lead to erroneous results.
5. All surfaces should have high reflectance to minimize radiation losses.
6. Water equivalent of the calorimeter assembly should be small to ensure
maximum rise in temperature of water following ignition.
5. DESCRIPTION:
Essentially the apparatus consists of the following parts :
BOMB : The bomb consists of three parts viz. Bomb body, lid and Union nut
The Bomb vessel and the lid are machined from an ultra strong corrosion
resistant stainless steel alloy rod, containing Cr, Ni & Mo and satisfying
special ringing and bending tests for intercrystalline corrosion.
The Bomb body is a cylindrical vessel having a capacity of 303 ml. The walls
are strong enough to easily support the normal operating pressure ( 30
atmospheres) and also extreme pressures as high as 300 atmospheres. During
burning at high pressures the Nitrogen & Sulphur contents are oxidized to
their respective acids. The corrosion resistant nature of the Bomb material
protects it from the corrosive vapours. The lid is provided with two
terminals. Two metallic rods pass through these terminals. One of which is
provided with a loop for placing the sample crucible and the other with a
4

groove. The method of attaching fuse wire is given in Section 7. Each rod is
also provided with a ring to press the fuse wire that attached to it.
The upper side of the lid is also provided with a small hook for lifting it and
with a Schrader valve for filling Oxygen in the Bomb. The Schrader valve is
provided with a metallic cap.
EACH BOMB IS TESTED FOR ITS PERFORMANCE AS PER THE
REQUIREMENTS OF THE INSTITUTE OF PETROLEUM
( IP12 / 63T). THE TEST IS CONDUCTED AT A PRESSURE OF 300
ATMOSPHERES AND THE PRESSURE IS MAINTAINED FOR A PERIOD OF
10 MINUTES WITHOUT ANY SIGN OF LEAKAGE.
WATER JACKET: It is made of Stainless steel and is highly polished on the
outside and also inside to minimize radiation losses. The top of the jacket
carries a rod to hold the stirrer unit, a hole to insert the temperature probe
and a small pipe through which water is added. This pipe also supports the
thermometer for measuring temperature inside the jacket.
OPTIONALLY
Jacket with top cover is provided with special highly insulated material to
make temperature radiation practically nil. With this provision, Temperature
correction to get the final and correct results is not required. This provision
also eliminates the water pipe and jacket thermometer. This jacket is
essential when the system is supplied with RS232C interface and related
software.
OFFSET STIRRER: It consists of a stirrer with fan driven at a constant
speed of 800 rpm by a motor through a heat insulator rubber belt. The motor
unit is kept at a sufficient distance from the vessel to eliminate radiative
heating and a heat insulator Bakelite divides the two parts of the stirrer rod.
This arrangement does not raise the temperature of the water by even 0.01 oC
in ten minutes, thus easily meeting the specific requirements laid down by the
British Standards Institution and the Institute of Petroleum and accepted
by the Indian Standard Institution. The electric supply for the stirrer motor
is obtained through the terminals provided on the Digital firing unit.
CALORIMETER VESSEL : It is made of copper and is brightly Ni-Cr plated
outside.
5

DIGITAL DIFFERENTIAL TEMPERATURE / FIRING UNIT (DDT/FU) : This

eliminates the requirements of
a. Beckman Thermometer
b. Vibrator
c. Timer
d. Illuminator with Magnifier
The Digital Differential Temperature / Firing Unit with electronic Timer
Beep have the following features:
Temperature Indication
3 Digit Digital display
Differential Temperature range
0 - 10C
Reading Accuracy of temperature
0.01C
Firing Voltage for Bomb
12 V AC
LED Indication for filament continuity
LED Indication for Bomb Combustion
Further details about the connection setting & operation of DDT/FU please
see section no. 13
PRESSURE GAUGE WITH FINE REGULATING VALVE : An accurate
pressure gauge is supplied for the measurement of pressure of Oxygen in the
Bomb. The dial is graduated from 0 to 70 Kg./Cm 2 ( 0 to 1000lb./in 2).
Normally the Oxygen is filled in the Bomb at a pressure of 25kg/cm 2 . It is
attached with copper tube to connect it with Oxygen gas cylinder and Bomb
for filling the oxygen gas.
GAS RELEASE VALVE : It is used to release the pressure of gases in the
bomb and also to collect gases after firing. It is screwed on the Schrader
Valve provided on the lid of the bomb. The knob should be turned down
clockwise to release excess of Oxygen gas out of the tube.
PELLET PRESS : It has a 8 mm diameter punch and die. Coal or other
powdered samples are compressed into pellets before weighing and burning.
This retards the burning rate and tends to retain the particles in the capsule,
thereby reducing the chances for incomplete combustion. The pellets are
6

easier to handle than loose samples. The pellets should not be made very
hard as excessive hardness leads to bursting upon ignition consequent with
incomplete combustion.
CRUCIBLE: Nickel alloy crucibles are offered as standard with the
instrument. Quartz, Platinum and Stainless Steel crucibles are being offered
as optional.
IGNITION WIRE: Nichrome wire is supplied with the instrument. Platinum as
an option.
6. REAGENTS, SAMPLES & SAMPLE HOLDERS,STANDARD SAMPLES:
BENZOIC ACID: It is commonly used as a calorific standard(6319 20cal/gm.
It burns easily and completely and can be compressed into pellets.
NAPHTHALENE: It is sometimes used as a combustion standard. It is not
hygroscopic but due to its volatility it is necessary to use with care to avoid
errors from sublimation.
SUCROSE OR CANE SUGAR: It is also used as a standard sample and as a
combustion aid. This material is neither volatile nor strongly Hygroscopic but
it is rather difficult to ignite and sometimes does not burnt completely. The
crystalline material should be ground to a powder before using.
STANDARD ALKALI SOLUTION: The washing from an Oxygen bomb test
must be titrated against a standard alkali solution to determine the acid
correction. A 0.1 N Sodium Carbonate solution is recommended. This is
prepared by dissolving 5.2996 grams of Na 2CO3 in water and diluting to one
litre. Sodium Hydroxide or potassium hydroxide solutions of the same
normality are acceptable. If Sulphur is present in the sample other reagents
as described in article 11 are required.

METHYL ORANGE OR METHYL RED INDICATORS: These are the usual

indicators used for acid alkali titrations.
ALLOWABLE SAMPLE SIZE: Care should be taken to avoid overcharging the
bomb. The mass of combustible charge ( sample plus combustion aid) should
7

not be more than 1.10 grams. When starting tests with new or unfamiliar
materials, it is always best to use samples of less than one gram. Not more
than 10,000 calories should be liberated in any tests and it is advisable to
work with mass liberating less than 7000 calories.
SELECTION AND PREPARATION OF SOLID SAMPLES:It is necessary that
solid samples be air-dry and ground until all particles pass through a 60 mesh
screen. The particle size is important because the combustion reaction
proceeds to completion with in a few seconds, and if any of the individual
particle is too large it will not burn completely. A sample that is too finely
divided may also be difficult to burn because extremely small particles can be
swept out of the combustion capsule by the turbulent gases, and if it fall to
the bottom of the bomb without being ignited, the test will give erroneous
results. Toshniwal pellet press offers a possible solution to the problem of
incomplete combustion in the cases of finely divided samples.
ANTHRACITES AND COKE : While testing anthracite coals, coke or other
material of slow burning characteristics, it may be difficult to secure ignition
and complete combustion of the entire sample. In these cases, the sample is
ground fine enough to pass through IS Sieve 20 ( 211 microns).
A small weighed amount of a standard combustible material such as powdered
benzoic acid should be mixed with such samples to facilitate combustion.
FOOD STUFFS AND CELLULOSIC MATERIALS: The high moisture content
of most food stuffs will usually require that these be dried before calorific
tests. The operator will have to select a method for preparing the sample
that will not destroy or remove any of the combustible constituents. It may
be necessary to make several preliminary tests to determine the approximate
maximum allowable moisture content at which the samples can be ignited in
the bomb without difficulty.
GELATINE CAPSULES: Volatile liquid samples to be burnt in an Oxygen Bomb
can be weighed and handled in gelatin capsules. The capsules consist of two
cups, which telescope together with a fraction fit adequate to retain most
liquids. Correction must be made for the heat of combustion of the gelatin
when used in calorimetry. Please also see section no.15
8

HEAVY OILS : Oils and other liquids which are non volatile at room
temperature can be weighed directly in to crucible. The loop of the fuse
should be positioned just above the surface of the sample. Non volatile liquids
can also be weighed and handled in gelatin capsules.
EXPLOSIVE AND HIGH ENERGY FUELS: Special precautions must be
observed when testing materials which release large volumes of gases upon
ignition or which detonate with explosive force. It is possible to test many
slow burning gun powders and rocket propellants in conventional bombs, but
the user must understand that these bombs are not designed to withstand
the shock pressure produced by certain primers and other mixtures which
detonate with explosive force. It is much safer to test these in a special high
pressure oxygen bomb.
Each new explosive sample or high energy fuel introduces special problems,
which can be solved only by careful experimentation. Usually it will be well to
observe the burning of a small amount of a sample over an open flame to
determine the explosive behaviour and then to proceed to bomb combustion
using only one -tenth or one-fifth of the usual amount of sample. Further
increases up to the 10,000 calories maximum permissible should be made
gradually, and only after all evidences indicates the absence of violent
behaviour.

7. SETTING UP AND ASSEMBLY:

GENERAL ARRANGEMENT : The lab in which the calorimeter is to operate
should be equipped with many of the facilities commonly used for chemical
analysis. These include desk space, running water, an analytical balance,
apparatus for making volumetric titrations and miscellaneous items of lab
ware. The calorimeter should be used in a room where fluctuations in
temperature can be avoided. In particular,the instrument should not be taken
from one chamber to another chamber maintained at a different temperature
immediately before use. Sufficient time must be allowed for equalization of
temperature throughout the jacket before starting to use the calorimeter.
All parts of the calorimeter should be kept clean and dry, and the inside of
9

the jacket should be wiped clean to remove any moisture which may have
condensed on the walls. Before starting to use a new calorimeter it is
advisable to assemble all parts of the apparatus without a charge in the bomb
and without water in the bucket and be sure that everything is in perfect
working order.
ASSEMBLY OF CALORIMETER PARTS: Place the star support (PVC) at the
bottom of the jacket and set it so that the leg having hole is fitted in the
slot provided at the base of the water jacket. Place the bucket on the star
supporter so that the pin outside of the bucket is fitted in the hole of the
leg of the star support. Place the star
( metallic) in the bucket in such a way that none of the arm comes within the
slot provided in the bucket. Lift the bomb on its stand by hook and place it on
the star ( metallic) clips inside the bucket. Attach the supply connections to
the electrodes provided on the lid of the bomb. Place the combined lid of
bucket and outer jacket in such a way that a pin provided on the cover plate
of the jacket fits into the smaller groove provided in the lid.
Mount the stirrer assembly on the stirrer rod provided on the cover plate of
the calorimeter jacket, passing the stirrer pipe through the opening provided
in the combined lid of bucket and the outer jacket. The connecting leads
attached with terminals provided on the bomb lid are now connected to the
two terminals provided on the cover of the calorimeter jacket. The
connections are then further taken to the Digital Differential Temperature /
Firing Unit (DDT/FU). Similarly stirrer connections are also connected to
DDT/FU which is further connected to the AC Mains ( 230 Volts, 50 Hertz).
ATTACHING THE FUSE: All manipulations prior to closing the Bomb can be
performed by holding the bomb lid in the support stand. Cut a single length of
7.5 cm of fuse wire and attach it to the electrodes.
It is not necessary to submerge the wire in a powder sample. In fact, better
combustion will usually be obtained if the loop of the fuse is set slightly
above the surface. When using pelleted samples, bend the wire so that the
loops bears against the edge of the pellet firmly enough to hold it against the
side of the capsule. In case of liquid fuels, the capsule should be held as a
loop of this wire. It is also a good practice to tilt the capsule slightly to one

10

side so that the flame emerging from it will not impinge directly on the top of
the straight electrode.
PLATINUM FUSE ARRANGEMENT: Platinum fuse wire can be attached to
the electrodes in the manner described above but most Platinum wire ignition
procedures require cotton or nylon thread to carry on ignition flame to the
sample. Wind out five turns of wire around a 2 mm diameter rod and then
removing the rod will forms a coil. The resulting coil is then connected
between the electrodes and arranged to one side of the cup with the axis of
the coils pointing towards the sample. A short length of thread is then
inserted through the coil and into the crucible.
WATER IN THE BOMB: Place 2.0ml.of distilled water in the Bomb from a
pipette.
FILLING THE BOMB WITH OXYGEN: While closing the Bomb, always make
certain that the head gasket or the sealing ring is in good condition and care
must be taken not to disturb the sample. Commercial Oxygen produced by
rectification of liquid air can be used directly from the supply cylinder.
To attach the filling connection, place the bomb on its stand. Put the high
pressure valve ( Fine Regulating Valve) in oxygen cylinder outlet and connect
the copper tube to the pressure gauge and pressure gauge to filling tube and
filling tube to bomb valve and make the connections perfectly tight. Open the
filling connection control valve of the cylinder slowly slowly. Observe the
gauge and allow the pressure to rise until the desired point ( about 25
atmosphere), then close the collection of gas control valve. To decrease the
pressure of bomb the gas release valve can be used. By rotating the gas
release valve in anti clockwise direction, the pressure can be reduced to the
desired point.
FILLING WATER IN THE BUCKET: On an accurate balance determine the
weight of the completely dry bucket, then added 2000 grams
( 0.5) of distilled water. Prior to weighing, the water should be brought to a
temperature about 2oC below that of the calorimeter jacket. This initial
adjustment generally will ensure a final temperature slightly above that of
the jacket. The calorimeter water should be cooled or heated in an auxiliary
11

container and not in the calorimeter bucket. The operator must also make
sure that there is no moisture on the outside surface of the bucket when it
is placed in the jacket.
8. OPERATING THE BOMB CALORIMETER:
Accurately weigh about one gram of the air dried material ground to pass
through IS Sieve 20 ( 211 microns) in the crucible. If required, sample can be
compressed in to a pellet before weighing.
Stretch a piece of firing wire ( generally Nichrome wire) across the
electrodes with in the bomb. Tie about 5.0 cms length of sewing cotton
around the wire, place the crucible in position and arrange the loose ends of
the thread so that they are in contact with the material. Use the same length
of thread in each determination. Pour 2 ml. Of distilled water in the bomb.
Reassemble the bomb, screw home with the fingers. Finally tightening it as
necessary, avoid excessive pressure. Charge the bomb slowly with oxygen
from a cylinder to a pressure of 30 atmospheres with out displacing its
original air content. Close the valve effectively, using as little pressure as
possible to detach the bomb from the oxygen supply. Weigh in to the
calorimeter vessel a quantity of the water to sufficient to submerge the nut
of the bomb to a depth of at least 2 mm leaving the terminals projecting. Use
the same weight of water in all tests. Transfer the calorimeter vessel water
jacket, lower the bomb carefully into the calorimeter vessel and having
ascertained to be gas tight. Connect it to the ignition circuit through a switch
for subsequent firing of the charge. Adjust the stirrer, place the
thermometer and covers in position and start the stirring mechanism. Wait
for ten minutes to stabilise the temperature and if it is not stable in ten
minutes then extend the period for another 5 minutes. For exact operation
please see SECTION NO. 13.
Determine the rate of change of temperature in the after period
( which follows the chief period by taking readings at 1 minute intervals for
at least five, preferably ten minutes.)

12

NOTE: It is desirable to keep the jacket temperature and the room

temperature as close to the calorimeter temperature as possible. The jacket
and room temperature should therefore be recorded.
Remove the bomb from the calorimeter and after a lapse of about half an
hour from the time of firing allowing the acid most to settle, release the
pressure by opening the valve. Verify that the combustion has been
completed by noting the absence of any sooty deposit with in the bomb. The
presence of any trace of sooty deposit indicates incomplete combustion and
invalidate the test.
Wash out the contents of the bomb with hot distilled water into a hard glass
beaker washing the bomb cap and the crucible. Add a measured excess, say
25 ml. Of 0.1 N Sodium Carbonate solution and boil it down to 16 ml to
convert any metallic sulphates or nitrates to the less soluble carbonate or
hydroxide. The consumption of alkali carbonate is equivalent to the sulphates
or nitrates together with the free sulphuric acid and nitric acids. Filter wash
and make up to 100 ml. To determine the Sulphur content take 50 ml portion
of this solution and follows the methods as given in section 11.
Determine the total acidity by titrating a 50 ml portion with 0.1 N
Hydrochloric acid using methyl orange as indicator. The titre representing
the excess alkali in one half of the quantity of sodium carbonate solution
added to the washings.
9. STANDARDIZING THE CALORIMETER:
DEFINITION: The water equivalent in this weight of water which is
equivalent in effective heat capacity to the entire system
( calorimeter vessel containing a specified weight of water, calorimeter bomb
charged with oxygen, fuel and water, DDT/FU and stirrer). Since the
specific heat of water is 1.000 0.002 cal/gm0C in the range of 100 to 400C,
the water equivalent is app. Equals to the effective heat capacity ( cal/ 0C),
the factor that is determined experimentally. Since the true water
equivalent is not required and is never evaluated, it is the effective heat
capacity which should be considered. The effective heat capacity is the heat
required to effect unit temperature rise in the system under the conditions
13

of a calorimetric determination. The effective heat capacity has a

temperature dependency since the specific heats of the constituent parts of
the system vary with temperature. 25 0C has been chosen as the reference
temperature because of its use in thermochemical calculations and because
the specific heat of water in the range of 25 0 to 400C is constant within
0.002 cal/g0C.
PRINCIPLE: The effective heat capacity of the system is determined by
burning pure and dry benzoic acid weighing not less than 0.9 and not more
than 1.1 gm. determine the corrected temperature rise T from the observed
test data, also titrate the bomb washings to determine the nitric acid
corrections, and measure the unbent fuse wire, compute the energy
equivalent by substitution in the following equation:
HM +E1 +E2
W = ---------------T
Where
W = Energy equivalent of calorimeter in calories per degree centigrade
H = Heat of combustion of standard benzoic acid in calories per gm.
M = Mass of standard benzoic acid sample in grams
T = Corrected temperature rise in degrees centigrade
E1 = Correction for heat of combustion of threads in calories
E2 = Correction for heat of combustion of firing wire in calories.

EXAMPLE
9.1

Standardization with a 0.995 gms benzoic acid sample ( 6319 cal/gm)

produced a net corrected temperature rise of 2.60 0C. The 5 cm ( 18.4
14

mg) of Nichrome wire and 8 cm ( 5 mg) of cotton thread were

consumed in the firing.
Substituting in the standardization equation:
H = 6319 cal/gm
M = 0,995 gm
E1 = ( 18.4 mg) ( .335 cal/mg)
E2 = ( 5mg) ( 4.180 cal/mg)
= 6.2 + 20.9=27.1 cal.
T = 2.609
(6319) (0.995) + 27.1
6287.405 + 27.1
6314.505
W = ---------------------------- = -------------------- = -------------2.60
2.60
2.60

W =2428.65 cal/0C
NOTE: Calorific value of Nichrome wire of 36 SWG ( diameter .0193 cm) is
0.82 cal/cm

10. DISCUSSION :
In determination of calorific value, principle observation is that of
temperature rise which when corrected and multiplied by the effective heat
capacity at the mean temperature of the chief period gives the heat release.
Further allowance is necessary for three sources of variable heat change
( the cooling loss, the Sulphur correction and the nitrogen correction) and
under certain circumstances for a source of constant heat gain ( the heat of
firing due to cotton and wire). The variable sources of heat change must be
allowed for in each test,but the source of constant heat gain can be treated
as one correction and under specified conditions neglected. It is convenient
to calculate the cooling loss as a temperature rise. The correction is
multiplied by the appropriate effective heat capacity to get the total heat
release. To the heat release so calculated, the corrections for Sulphur,
15

nitrogen and, if necessary, for the source of constant heat gain are applied to
give the true heat release.
10.1 PRECAUTIONS:
The operator must follow the following basic points in order to operate this
oxygen bomb safely:
a. Do not use too much sample. The bomb cannot be expected to withstand
the effects of combustible charges which liberate more than 10,000
calories. This generally limits the total weight of combustible material
( sample +gelatin, firing oil or any combustible aid) to not more than
1.10gm. Do not charge with more oxygen than is necessary and do not fire
the bomb if an overcharge of oxygen should accidentally be admitted.
b. Keep all parts of the bomb, especially the insulated electrode assembly in
good repair at all times. Do not fire the bomb if gas bubbles are leaking
from the bomb when it is submerged in water.
c. Stand back from the calorimeter for at least 15 seconds after firing and
above all, keep clear of the top of the calorimeter. If the bomb explodes,
it is most likely that the force of explosion will be directed upwards.
d. Proceed with caution and use only a fraction of the allowable maximum
sample when testing new materials which burn rapidly, or which have
explosive characteristics.
10.2

CAUSES OF POOR COMBUSTION:

An incomplete combustion in the oxygen bomb is nearly always due to one or

more of the following causes:
a. Excessively, rapid admission of gas to the bomb during charging, causing
part of the sample to be blown out of the cup.
b. Loose or powdery condition of the sample in the cup prior to ignition
causing ejection due to violence of combustion.
c. The use of a sample containing coarse particles which can not burn readily
with coal, such particles are usually too large to pass through a 60 mesh
screen.
d. The use of a sample in the form of pellet which has been made too hard
causing spilling and the ejection of fragments during heating.
16

e. Use of an ignition current too low to ignite the charge or too high causing
the fuse to break before combustion is well under way.
f. Insertion of the fuse wire loop below the surface of a loose sample. Best
results are obtained by barely touching the surface of the sample or even
hanging the wire slightly above the surface.
g. Use of not enough oxygen to burn the charge completely or conversely,
the use of a very high initial gas pressure which may retard development
of the required turbulence during combustion.
10.3

SOURCE OF CONSTANT HEAT GAIN:

a. Cotton : Determine the weight, after drying at 105 0C, of a known length of
cotton and using the calorific value of cellulose ( 4180 cal / g), calculate
the heat release from the standard length.
b. Firing Wire: Determine the weight of a piece of wire equal in length to
the distance between the poles of the bomb and calculate the heat
release by allowing for Nickle chromium 3.35 cal and for platinum 1.0
cal / 0.01gm.
c. The sum (q) of these is usually about 20 40 cal and is constant for all
determinations. If the heat releases from benzoic acid in the
determination of the heat capacity is Q cal and from the fuel under test
is H cal, the error in the value of the heat release calculated using the
apparent heat capacity and ignoring the source of constant heat gain is :

q ( H Q )
------------if H=Q, q=0, so that, if a standard heat release
Q
is maintained, the effect of the source of constant heat gain is eliminated by
using the apparent heat capacity calculated as described earlier.

10.4

COOLING CORRECTION:

The cooling correction includes the effect of the heat interchange between
the vessel and the jacket, due top conduction, convection and radiation and of
the heats of stirring and evaporation. This is minimized by having : (a) the
17

temperature of the water in the vessel below that of the water in the jacket
at the time of firing and within 1.0o C, preferably 0.5o C, of it at the end
of the chief period. (b) a low heat of stirring and (c)a low loss by evaporation.
The correction may be applied by the use of Regnault Pfaundler formula or
the Dickinson formula. In determining the water equivalent the same formula
has to be used. No cooling correction is necessary when using SPECIAL
INSULATED JACKET OR ADIABATIC TYPE JACKET, provided that the
thermal conditions of the determination are substantially the same as those
in the determination of the heat
capacity, that is the firing temperature and heat release are app. Constant
and the length of the chief period is fixed. We here under give Dickinson
correction formula as Regnault Pfaundler ( R-P) correction formula is very
cumbersome and is difficult to understand and apply.
Dickinson Correction: It should also be applied for finding the water
equivalent or the heat capacity of the apparatus.
Cooling correction = v ( Ta T0 ) + v ( Tn Ta)
Where v = rate of fall of temperature per minute in the preliminary period
( if the temperature is rising during this period then v is negative)
, v = rate of fall of temperature per minute in the after period
Ta = The time in minutes at temperature t0= 0.60( t
10.5 SULPHUR CORRECTION :
This takes into account the extra heat released in the bomb where, under
pressure and in the presence of Oxides of nitrogen and water, the Sulphur in
the fuel is converted into sulphuric acid. The correction in the difference
between the heat released due to this and that due to the conversion of the
Sulphur into gaseous Sulphur dioxide, it amounts to 22.5 cal for 0.01 gm
Sulphur ( one percent on one gram of fuel). The Sulphur correction may be
made using the Sulphur content determined by the Eschka method or
Strambi method.
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10.6

NITROGEN CORRECTION :

The nitrogen correction takes account of the fact that part of the nitrogen
of the fuel and of that in the air originally present in the bomb is converted
into nitric acid in the bomb. The correction is the heat released due to the
reaction which does not occur at atmospheric pressure, it amounts to 1.43 cal
per milliliter of 0.1 N nitric acid formed. Since it has been shown to be
constant for a constant heat release in a given bomb when burning bituminous
coals and benzoic acid, it may be assessed when determining the effective
heat capacity that only nitric acid being present in the washings. A
determination of nitric acid must be made when testing an anthracite. When
determining it after the combustion of a fuel, the acidity due to nitric acid is
the difference between the total acidity and that due to sulphuric acid ( 0.01
g of Sulphur 6.25 ml. Of 0.01 N sulphuric acid)
Nitric acid : if a ml. Of 0.1 N hydrochloric acid is used in the titration the
total acidity due to nitric and sulphuric acid together is equivalent to ( 50 a
)ml of 0.1 N acid and the amount of nitric acid present is equivalent to :
S
( 50 a ) ---------- = n ml of 0.1 N nitric acid
0.0016
Here we have assumed that 50 ml of 0.1 N alkali ( Sodium carbonate
solution) has been used and S is the amount of Sulphur in the sample in
grams.

10.7

APPLICATION OF CORRECTIONS:

To correct the calorific value as determined in the bomb calorimeter to that

which would be obtained by the complete combustion of the coal in the air,
deduct 1.43 cal for each milliliter of 0.1 N nitric acid produced and 22.5
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calories for each 0.01 gm of Sulphur found from the total calories developed.
Whilst the cooling correction is added in both the determination of water
equivalent and of the calorific value of a fuel, the cotton corrections, the
heat of firing, the Sulphur and nitrogen corrections are subtracted from the
observed calorific value, though such corrections as are appropriate were
added to the heat release from the benzoic acid to determine the water
equivalent. The calorific value should, if necessary, be corrected using the
moisture content determined at the same time as the calorific value, to the
same moisture content as that reported for the proximate analysis.
10.8

ROUNDING OFF:

Round off the mean of the values or the single value to the nearest 10 cal/g
10.9

TOLERANCES:

The results of the duplicate determinations in one laboratory should agree to

within 100 cal/g and those between different laboratories to within 125
cal/g.

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DETERMINATION OF SULPHUR IN COMBUSTIBLE SOLIDS:

Allow the bomb to stand in the water bath for at least 10 minutes after
firing ( if calorific value of the sample is to be determined in the same test,
the temperature must be recorded as describe earlier). Release the residual
gases slowly and at an even rate so that the pressure is reduced to
atmospheric level in not less than one minute. Open the bomb and wash all
parts of its interior, including the combustion capsules, valve passages and
electrodes with a fine jet of distilled water containing 1 ml of a saturated
solution of methyl orange indicator per litre. Wash until no acid reaction is
observed, collecting the washings in a beaker.
Add a measured excess, say 50 ml of 0.1 N sodium carbonate solution and boil
to convert any metallic sulphates or nitrates to the less soluble carbonates or
nitrates together with the free sulphuric and nitric acids. Filter, wash and
make upto 100 ml. If calorific value is to be determined keep 50 ml portion
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aside to determine the total acidity. To determine Sulphur content neutralize

the 50 ml portion with concentrated hydrochloric acid and add one ml in
excess. Boil for five minutes to remove carbon dioxide and add concentrated
ammonia solution until the liquid is neutral to methyl orange. Add one milliliter
of concentrated hydrochloric acid.
Make up the volume of the solution to app. 150 ml with distilled water. Cover
the beaker and heat until the solution boils and then reduce the heating
slightly until ablution ceases. Then add with a delivery time of app. 20
seconds, 5 ml of 10% barium chloride solution from a pipette held so that the
barium chloride falls into the middle of the hot solution which is being
agitated. Keep the solution just below boiling point for 30 minutes. BaSO 4
precipitate will appear. Filter the solution using ashless whatmann filter
paper in a fluted long stemmed 600 funnel.
Transfer the paper and precipitate to a weighed crucible, dry at low heat,
char the paper without flaming, then raise the temperature to a good red hot
9 app. 9250C )and heat to constant weight. If the crucible is placed in a cold
electric muffle furnace and the current turned on , drying, charring and
ignition will usually occur at the desired rate. After ignition is completed,
allow the crucible to cool to room temperature and weigh. Determine the
exact weight of the barium sulphate precipitate and calculate the percentage
of Sulphur in the sample as :
Wt. BaSO4 x 13.734

Sulphur%

= -----------Wt. of sample

12 . DETERMINATION OF SULPHUR IN COMBUSTIBLE LIQUIDS

For oils or other liquids containing 5% Sulphur or less, use a sample weighing
from 0.6 to 0.8gm. If the sample contains over 5% Sulphur use a sample
weighing from 0.3 to 0.4 gm and add an equal amount of Sulphur free U.S.P.
white oil. If the sample is not readily miscible with white oil, some other low
combustible diluent may be used. However , the combined weight of sample
and white oil or other combustion aid MUST NOT exceed 10 grams. If the
sample is volatile it must be weighed in a sealed holder.
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13. OPERATING INSTRUCTIONS FOR DIGITAL DIFFERENTIAL

TEMPERATURE / FIRING UNIT ( DDT/FU)
The DDT/FU consists of the firing unit along with the Digital temperature
Indicator and timer. Set the DDT /FU as follows:
1. Set the Bomb Calorimeter as per the serial No. 7
2. Insert the RTD Probe into the Bomb Calorimeter through the combined
lid
3. Connect the RTD Probe to the DDT/FU terminal marked PROBE
4. Connect the DDT/FU terminal to the Bomb Calorimeter terminal on the
water jacket.
5. Attach the stirrer connection to DDT /FU
6. Switch ON the instrument and stirrer.
7. LED of the DDT/FU will glow which shows that the proper placement of
filament is done inside the bomb.
8. Timer will start giving beeps after app every one minute.
9. Adjust the fine and coarse control knob for ZERO setting or set at 1.00
10. Wait for 10 minutes to stabilise the initial temperature. If temperature
is not stabilise extend the period for another 5 minutes for stabilisation.
11. Record the primary period ( initial ) temperature
12. Press the push button marked FIRE. Please note that LED will be OFF
after the firing has been done. This shows that the firing has taken place
13. After firing, note down the chief period temperature after every beep
given by timer.
14. Record the temperature reading till there is no further rise in
temperature
15. Find out the rise in temperature ( Sr. No. 14 Sr. No.11)
16. Switch OFF the instrument and stirrer.
17. Now calculate the calorific value of the sample.

14.

In adiabatic Bomb or water jacket with highly insulated material,

temperature correction factor is not required and if nitric and sulphuric
correction factor is ignored then calorific value of a sample can be calculated
by the following formula:
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W x T ( E1 + E2)
Calorific value H = ------------------------------------M
Where W is the water equivalent
T is the rise in temperature
E1 is the calorific value of thread
E2 is the calorific value of Nichrome or Platinum wire
M is the mass of the sample

15. METHOD WITH GELATIN CAPSULE

In this case after calculating the water equivalent, place empty capsule of
known weight and find out the calorific value of capsule as per above formula.
Take another capsule and weigh it correctly. Filled the capsule ( do not fill
the capsule completely) with the liquid sample and reweigh it to know the
mass of the sample. Perform the experiment and note down the rise in
temperature. Find out the calorific value as
W x T ( E1 + E2) E3 x M1
Calorific value H = ------------------------------------M2 M 1
Where E3 is the calorific value of empty capsule
M1 is the mass of empty capsule
M2 is the mass of capsule + sample.

We also supply the system with RS 232C interface and related software to
attach with PC to get the automatic calculation of calorific value. For details
please contact

Toshniwal Technologies Pvt. Ltd.

23

B-48, Phase I
Mayapuri Industrial Area,
NewDelhi-110064 India
Tel : 011-45612992,28114425
fax ; 011-45612993
e mail : factory@toshniwaldelhi.com

Concerned person : Mr K.MURARI( 09868758811)

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