Aim: To calculate the calorific value of a liquid/solid fuel by bomb calorimeter.

Theory: Heat released in a chemical reaction can be determined experimentally by using an adiabatic calorimeter. The reaction must proceed without any side reactions and sufficiently fast that the heat exchange with the surroundings is negligible. The heat of combustion can be most conveniently measured using an adiabatic bomb calorimeter (see Figure 1). In such calorimeter, the combustion reaction occurs in a closed container under constant volume (bomb). The bomb is immersed in a weighted quantity of water and surrounded by an adiabatic shield that serves as a heat insulator. Continuous stirring ensures that heat is distributed evenly in the calorimeter. The bomb and the water bath, which are in direct thermal contact, constitute an adiabatic bomb calorimeter. In this experiment the heat of combustion of an organic compound is determined using a commercial Parr adiabatic bomb calorimeter. The heat of combustion is directly related to important quantities such as the internal energy and enthalpy of a chemical reaction.

Figure 1 Bomb calorimeter The methods used to determine the calorific value of fuels are based on calorimetry and vary according to the type of fuel and the degree of accuracy required. The calorific value of solid and liquid fuels is usually calculated using a bomb calorimeter. A known weight of the solid or liquid fuel is exploded electrically in a stainless steel bomb charged with oxygen at 25 atmospheres. The bomb is immersed in a known weight of water in a calorimeter so that the heat
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released on combustion is transmitted to the water. The temperature of water is measured accurately as a function of time so that the actual rise in temperature due to the burning of the fuel may be evaluated graphically by interpolation. To minimize heat losses, the calorimeter is surrounded by an air jacket. The change in temperature in the water bath provides the calorific value of the fuel. The general equation of calorific value by the bomb calorimeter is: Where E = Calorific value if fuel sample C = Water equivalent energy T= Rise in temperature e = error due to wire burning m = mass of fuel sample

(1)

Setting up and assembly: General Arrangement 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 through the jacket before starting to use the calorimeter. All parts of the calorimeter should be kept clean and dry, and the inside of 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 supports (PVC) at the bottom of the jacket and see it so that the leg having hole is fitted in the slot provided at the base of the water jacket. Place the bucket on star supporter so that the pin outside 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 arms comes within the slot provided in the bucket. Lift the bomb in on its stand by hook and place it on the star (metallic) in

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the bucket. Attach the supply connection to the electrodes provided on the cover plate of the jacket fits into the smaller groove 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. 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 against the side of the capsule. In case of liquid fuels, the capsule should be held as a loop of this wire. It also a good practice to tilt the capsule slightly to one side so that the flame emerging from it will not impinge directly on the loop of the straight electrode. Water in the Bomb Place 2.0ml of distilled water in the Bomb from a pipette.

Procedure: 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 produce 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 connection perfectly tight. Open the filling connection control valve of the cylinder slowly slowly. Observed the gauge and allow the pressure to rise until the desire point (about 25 atmosphere), then close the connection of gas control valve. To decrease the pressure of the gas release valve can be used. By rotating the gas release valve in anti clockwise direction, the pressure can be reducing to the desired point.
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Filling Water in the Bucket On an accurate balance determine the weight of the completely dry bucket, then added 2000 grams (0.50) of distilled water. Prior to weighing, the water should be brought to a temperature about 2 C below that of the calorimeter jacket. The initial adjustment generally will ensure a final temperature slightly above that of the jacket. The calorimeter water should be cooled or heated in auxiliary container and not in the calorimeter bucket. The operator must make sure that there is no moisture on the outside surface of the bucket when it is placed in the jacket. There are two connecting leads out of them one connection form water terminal to bomb terminal and second from water terminal to firing unit terminal. 1. Fill the water up to the level of S.S. Ring of Bomb in the calorimeter vessel. Put the Black combined lid on the water jacket in particular direction. There is a small slot in combined lid and small pin in water jacket. Small pin of water jacket come in the small slot of combined lid. 2. Connect the two pin plug of stirrer in the socket which is in on the back side of Firing Unit and dip the stirrer pipe in the water which is in calorimeter vessel and tight with the screw of stirrer. 3. Tight the screw of stirrer with the pin which is on the top of water jacket is on the right side. 4. Connect the vibrator, Timer and Illuminator with magnifier. Connect the socket of magnifier which is also on the back side of the Firing Unit. 5. Tight the vibrator on the top of water threaded portion. 6. Dip the bulb of Backmen thermometer in the water through holding the Backmen thermometer in the clamp of vibration and not the initial temperature of Backment thermometer. 7. Press the Green Button to check the continuity if the bulb indicates it means the circle is complete then to push the red button far fire the sample. 8. After firing the sample heat will be generated this will transferred in the water of the calorimeter vessel.

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9. Note the rise temperature of Backmen Thermometer. The difference rise temperature initial temperature is the actual rise temperature of the sample. Observation Table: Compound mass in g init ti in C final tf in C T in K CV of fuel

Calculations: 2325 45

Conclusion: The calorific value of the _______________________ is ___________________.

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