TO DETERMINE THE CALORIFIC VALUE

ADITYA; ANIL YADAV; DEVANAND

INTRODUCTION:

Calorific value is defined as the amount of heat energy produced on complete combustion of
1 kilogram of a fuel. It is expressed in a unit called kilojoule per kg. The higher the calorific
value of a fuel, the more is its efficiency.

Table below shows calorific value of different fuels:

Fuel Calorific value

Hydrogen 150000
LPG 55000
CNG 50000
Methane 50000
Petrol 45000
Kerosene 45000
Diesel 45000
Biogas 40000
Coal 33000
Wood 22000
Cow dung 8000

Each kilogram of LPG produces much more heat than one kilogram of wood or coal. The
calorific value of LPG is the highest among wood, charcoal and LPG. In rural areas, cow dung
and wood are still used as fuel because these are very cheap and easily available.
Calorific Value = Heat Produced / Amount of Fuel used for burning in KJ/Kg

For Example, If 4.5Kg of fuel is completely burnt and amount of heat produced stands
measured at 1,80,000 KJ, What is the calorific value?

Calorific Value = 1,80,000 KJ / 4.5 Kg

= 40,000KJ/Kg

Hence Calorific value of fuel is calculated to 40,000 KJ/Kg

THEORY:

A bomb calorimeter is a device that is designed to measure the amount of heat that is given off
or taken in by a reaction. It is designed to be isolated from the surroundings, meaning that no
heat can leave or enter the device.
 FIG. A bomb calorimeter

In order to accomplish this, the outside wall of the calorimeter is a vacuum sealed wall similar
to an insulated mug you might carry coffee in. Inside the calorimeter is a vessel in which the
reaction occurs surrounded by a water bath. The temperature of the water bath can be monitored
via thermometer.
When a reaction takes place in the calorimeter, the temperature of the water bath changes. If
an exothermic reaction occurs, the water bath temperature goes up. If an endothermic reaction
occurs, the water bath temperature goes down.
In an ideal calorimeter all the heat exchange would take place with the water. However, in real
life, the materials from the calorimeter itself, the stainless steel, thermometer, etc., exchange
heat with the system as well. We can correct for this by using a heat capacity for the calorimeter
in our calculations.
Because all the heat is exchanged inside the calorimeter, we can set the total heat to zero. We
have three terms for the three parts of our calorimeter: the calorimeter itself, the water bath,
and the chemical reaction.

Other Types of Calorimeters:

There are many kinds of calorimeters, each designed for measuring the heat released by a
particular chemical process. Some examples include:
 Flame Calorimeter
The combustible gas is metered into the
calorimeter. Temperatures of all reactants
must be controlled. Since the reaction
occurs at constant pressure, DcombH is
measured directly.

Solution Calorimeter
Reactants are initially separated. The
temperature change is measured when they
are allowed to mix. Quantities that can be
determined include DmixH, DdilutionH,
and DsolvationH.

Calorimeter design is very tricky, especially for processes involving very small energy
changes, e.g., protein folding, or energy changes on top of a large background, e.g., excess heat
from "cold fusion". Heat leaks must be minimized, and all other heat generating processes
must be accounted for.

Purpose of Bomb Calorimetry Experiments:

Bomb calorimetry is used to determine the enthalpy of combustion, DcombH, for hydrocarbons:
CxHYOz (s) + (2X+Y/2-Z)/2 O2 (g) => X CO2 (g) + Y H2O (l)
Since combustion reactions are usually exothermic (give off heat), DcombH is typically
negative. (However, be aware that older literature defines the "heat of combustion" as -
DcombH, so as to avoid compiling tables of negative numbers!)
Construction of a Bomb Calorimeter:

The bomb calorimeter consist primarily of the sample, oxygen, the stainless steel bomb, and
water.
The dewar prevents heat flow from the calorimeter to the rest of the universe, i.e.,
qcalorimeter = 0
Since the bomb is made from stainless steel, the combustion reaction occurs at constant volume
and there is no work, i.e.,
wcalorimeter = -ò p dV = 0
Thus, the change in internal energy, DU, for the calorimeter is zero
∆Ucalorimeter = qcalorimeter + wcalorimeter = 0
The thermodynamic interpretation of this equation is that the calorimeter is isolated from the
rest of the universe.

PROCEDURE:
1. Prepare the sample in the bomb. The food sample is put in the crucible together with a piece
of cotton wool. A known length of fuse wire is passed through the sample with both ends of
the wire being attached to the 2 electrodes of the bomb.
2. Closing the bomb. Care must be taken not to disturb the sample when moving the bomb head
to the bomb cylinder. Check the sealing ring to be sure that it is in good condition and moisten
it with a bit of water so that it will slide freely into the cylinder; then slide the head into the
cylinder and push it down as far as it will go. For easy insertion, push the head straight down
without twisting and leave the gas release valve open during this operation. Set the screw cap
on the cylinder and turn it down firmly by hand to a solid stop. When properly closed, no
threads on the cylinder should be exposed.
3. Filling the bomb. Connect the oxygen supply to the bomb and close the gas release valve.
Open the filling connection control valve slowly and watch the gauge as the bomb pressure
rises to the desired filling pressure (usually 30 atm., but never more than 40 atm.); then close
the control valve.
4. Fill the calorimeter bucket. Put the bomb inside the calorimeter bucket by attaching the
lifting handle to the screw cap and lowering the bomb with its feet spanning the circular boss
in the bottom of the bucket. Handle the bomb carefully during this operation so that the sample
will not be disturbed. Remove the lifting handle and add 1.2 litres of water inside the bucket.
5. Final settings. Connect the power source to the bomb and put the thermometer inside the
bucket. Set the cover on the jacket and start the stirrer.
6. Read and record temperatures. Let the stirrer run for 5 minutes to reach equilibrium before
starting a measured run. At the end of this period start a timer and read the temperature. Read
and record temperatures at one-minute intervals for 5 minutes. Then, at the start of the 5th
minute...
7. Stand back from the calorimeter and fire the bomb.
8. Recording change in temperature. The bucket temperature will start to rise within 30 seconds
after firing. This rise will be rapid during the first few minutes; then it will become slower as
the temperature approaches a stable maximum as shown by the typical temperature rise curve
. Record temperatures at one minute intervals until the difference between successive readings
have been constant for 3 minutes. Usually the temperature will reach a maximum; then drop
very slowly. But this is not always true since a low starting temperature may result in a slow
continuous rise without reaching a maximum. As stated above, the difference between
successive readings must be noted and the readings continued at one-minute intervals until the
rate of the temperature change becomes constant over a period of 3 minutes.
9. Opening the bomb. After the last temperature reading, stop the motor and lift the cover from
the calorimeter. Lift the bomb out of the bucket and open the gas release valve on the bomb
head to release the gas pressure before attempting to remove the cap. After all pressure has
been released, unscrew the cap and lift the head out of the cylinder. Examine the interior of the
bomb for soot or other evidence of incomplete combustion. If such evidence is found, the test
will have to be discarded.
10. Fuse wire burnt. Remove all unburned pieces of fuse wire from the bomb electrodes;
straighten them and measure their combined length in centimeters. Subtract this length from
the initial length of fuse wire used and enter this quantity on the data sheet as the net amount
of wire burned - Lf.

∆U and ∆H in a Bomb Calorimeter

A). Internal energy change ∆U

Since the calorimeter is isolated from the rest of the universe, we can define the reactants
(sample and oxygen) to be the system and the rest of the calorimeter (bomb and water) to be
the surroundings.
The change in internal energy of the reactants upon combustion can be calculated from
Since the process if constant volume, dV=0. Thus, recognizing the definition of heat
capacity Cv yields

Assuming Cv to be independent of T over small temperature ranges, this expression can be

integrated to give

where Cv is the heat capacity of the surroundings, i.e., the water and the bomb.

B). Enthalphy change ∆H

By definition of enthalpy

Since there is very little expansion work done by condensed phases, D(pV) » 0 for solids and
liquids. Assuming the gas to be ideal yields

C). Intuitive difference between ∆U and ∆H

Recall that DU=qv is the heat flow under constant volume conditions, whereas DH=qpis the
heat flow under constant pressure conditions. The difference between these two situations is
that pV work can be done under constant pressure conditions, whereas no pV work is done
under constant volume conditions.
Consider the case where Dngas > 0. i.e., the system expands during the reaction. The same
amount of energy is released by the reaction under both sets of conditions. However, some of
the energy is released in the form of work at constant pressure; thus, the heat released will be
less than at constant volume. Mathematically,

In the case where Dngas < 0. i.e., the system contracts during the reaction, the surroundings does
work on the system. Thus, this work is available for energy release from the system back to
the surroundings in the form of heat. Mathematically,

These cases can be depicted pictorially as follows:

 Dngas > 0
work done by system
-∆H < -∆U or ∆H > ∆U

∆ngas < 0
work done on system
-∆H > -∆U or ∆H < ∆U

Calibration of the Calorimeter

A). Estimating Cv
The heat capacity of the bomb calorimeter can be estimated by considering the calorimeter to
be composed of 450 g water and 750 g stainless steel. Knowing the specific heat capacity of
water to be 1 cal/g·K and estimating the specific heat capacity of steel to be 0.1 cal/g·K
yields

B). Measuring Cv
For accurate work, the heat capacity of the calorimeter must be measured. This is done by
depositing a known amount of energy into the calorimeter and observing the temperature
increase. The two most common methods for measuring Cv are
1. Burning a standard with known DU, e.g., benzoic acid.
mbenzoic acid ∆Ubenzoic acid = mbenzoic acid -6318 cal/g·K = -Cv ∆T
2. Doing electrical work by passing current though a resistor.
∆U = w + q = V·I·t + 0 = Cv ∆T
 REFERENCES
⮚ http://www.chem.hope.edu/~polik/Chem345-2000/bombcalorimetry.htm
⮚ https://www.gpo.gov/fdsys/pkg/GOVPUB-C13-
e954af4b356cc3638f0e8456c440814b/pdf/GOVPUB-C13-
e954af4b356cc3638f0e8456c440814b.pdf
⮚ https://www.chegg.com/homework-help/questions-and-
answers/experiment-7-bomb-calorimeter-71-aim-determine-calorific-
value-given-fuel-72-apparatus-mah-q16808193