ME 2121-1 PART 1 DETERMINATION OF CALORIFIC VALUE OF FUELS (OXYGEN BOMB CALORIMETRY)

** Students are required to bring thumb drive to the laboratory session to download experimental data.

2013/2014

Department of Mechanical Engineering National University of Singapore

AS A SAFETY MEASURE, WEARING OF SHOES DURING EXPERIMENT IS MANDATORY.

WEARING ANY KIND OF SHORTS (e.g BERMUDAS, MINI SHORTS) ARE PROHIBITED. YOU ARE REQUIRED TO WEAR LONG PANTS DURING THE EXPERIMENTS.

TABLE OF CONTENTS

LIST OF FIGURES INTRODUCTION DESCRIPTION OF BOMB CALORIMETER THEORY PROCEDURE CALCULATION OF THE HEAT OF COMBUSTION CALCULATION/ RESULTS & DISCUSSION REFERENCES

(ii) 1 1 1 2 4 5 5

LIST OF FIGURES

Figure 1 Figure 2 Figure 3

The oxygen bomb calorimeter Tying of fuse wire loop Typical temperature time curve of a bomb calorimetric process

6 6 7

ii

INTRODUCTION
The bomb calorimeter is a classic device used to determine the heating or calorific value of solid and liquid fuel samples at constant volume. Basically, this device burns a fuel sample and transfers the heat into a known mass of water. From the weight of the fuel sample and temperature rise of the water, the calorific value can be calculated. The calorific value obtained in a bomb calorimeter test represents the gross heat of combustion per unit mass of fuel sample. This is the heat produced when the sample burns, plus the heat given up when the newly formed water vapour condenses and cools to the temperature of the bomb. Determining calorific values is profoundly important; fuels are one of the biggest commodities in the world, and their price depends primarily on their heating/calorific value. This experiments also demonstrates the First Law of Thermodynamics for a control mass. The bomb calorimetric study is carried out to gain a better understanding of the working principles of the bomb calorimeter and also to find out the gross calorific values of two types of liquid fuel.

DESCRIPTION OF THE PARR 1341 PLAIN JACKET OXYGEN BOMB CALORIMETER

Figure 1 shows the assembled parts of a Parr 1341 Plain Jacket Oxygen Bomb Calorimeter. The Parr 1108 oxygen bomb furnished with the 1341 calorimeter is a 342 ml pressure vessel with a removable head and a closure that can be sealed by simply turning a knurled cap until it is hand tight. Sealing forces develop internally when the bomb is pressurized, but after the pressure has been released the cap can be unscrewed and the head lifted from the cylinder. Two valves with replaceable stainless steel bodies are installed in the bomb head. On the inlet side, there is a check valve that opens when pressure is applied and closes automatically when the supply is shut off. On the outlet side, gases are released through an adjustable needle valve passing through a longitudinal hole in the valve stem and discharging from a short hose nipple at the top. Gas flow through the outlet valve is controlled by turning a knurled adjusting knob. A deflector nut on the inlet passage diverts the incoming gas so that it will not disturb the sample. A similar nut on the outlet side reduces liquid entrainment when gases are released.

THEORY
Consider a system that consists of the sample (s), the bomb (b), and the calorimeter water (w) and bucket. The sample is contained within the bomb, which is immersed within the water inside the bucket. Applying the First Law of Thermodynamics to this system gives
Q v W U

(1)

where U = the change in internal energy of the system QV = the heat transfer at constant volume W = work performed on or by the system Since there is no work crossing the system boundary, W = 0. If the entire system is adiabatic, the heat of combustion is used to change the temperature of the water and the bomb:

Qv

T mc dT v [(mcv )b (mcv ) w ] dT To To

(2)

Assuming constant specific heats

Q v [(mc v ) b (mc v ) w ]T

(3)

where T = total temperature change of the system. The heat transfer is also equal to the heat of combustion of the sample i.e.
Q v (mu ) S

(4)

In the case of a liquid fuel, the sample is composed of fuel (f), and fuse wire (fw). Therefore,
(mu ) f (mu ) fw [(mc v ) b (mc v ) w ]T

(5)

The heating value of the fuel can now be expressed as

uf [(mc v ) b (mc v ) w ]T (mu ) fw mf

(6)

EXPERIMENTAL PROCEDURE
(Please follow strictly the procedure listed below and observe the safety precautions highlighted). 1. Prepare the fuel sample by placing it in a capsule and weighing on a balance (sensitivity of the balance: 0.0001g). Ensure that the weight of the fuel does not exceed 1.1g. Note down the weight of the fuel sample (mf). 2. Set the bomb head on the A38A support stand and attach a 10cm long fuse wire, as shown in Figure 2. Bend the loop of fuse wire down just above the liquid fuel sample. The wire must not make contact with the fuel capsule.

3. Care must be taken not to disturb the sample when moving the bomb head from the support stand to the bomb cylinder. Be sure that the 104A2 contact ring is in place above the sealing ring and that the sealing ring is in good condition; then slide the head into the cylinder and push it all the way down. Set the screw cap on the cylinder and turn it down firmly by hand. Do not use a wrench or spanner on the cap. Tightening with hand should be sufficient to secure a tight seal. 4. Press the fitting on the end of the oxygen hose into the inlet valve socket and turn the union nut finger tight. Close the valve on the filling connection; then open or crack the oxygen tank valve not more than one-quarter turn. Open the filling connection control valve slowly and watch the gauge as the bomb pressure rises to the desired filling pressure (30 atmospheres); then close the control valve. Release the residual pressure in the filling hose by pushing downward on the lever 2

attached to the relief valve. The gauge should now return to zero. If too much oxygen should accidentally be introduced into the bomb, do not proceed with the combustion. Detach the filling connection; exhaust the bomb; remove the head and reweigh the sample before repeating the filling operation. 5. Fill the calorimeter bucket by first taring the dry bucket on a solution or trip balance; then add 2000 ( 0.5) grams of water. Note the exact mass of the water. 6. Set the bucket in the calorimeter; attach the lifting handle to the two holes in the side of the screw cap and lower the bomb into the water 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 handle and shake any drops of water back into the bucket; then push the two ignition lead wires into the terminal sockets on the bomb head using a tweezer, being careful not to remove any water from the bucket with the fingers. 7. Set the cover on the jacket with the thermometer facing toward the front. Turn the stirrer by hand to make sure that it runs freely; then slip the drive belt onto the pulleys and start the motor. 8. Let the stirrer run for at least 5 minutes to reach equilibrium before starting a measured run. As automated data logging is done for multiple experimental set-ups, the Laboratory Officer will commence scanning once all the groups have begun step (8). Take note of the w value that can be found on the calorimeter jacket. 10. The scanning of the temperature data is pre-set at every 10 seconds interval. At the start of the 10th minute, stand back from the calorimeter and fire the bomb when prompted by pressing the ignition button and holding until the indicator light goes out. Normally the light will glow for only about half a second, but release the button within 5 seconds regardless of the light duration. Caution: Do not have the head, hands or any parts of the body over the calorimeter when firing the bomb; and continue to stand clear for 30 seconds after firing. 11. The bucket temperature will start to rise within 20 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 shown in Figure 3. Accurate time and temperature observations must be recorded to identify certain points needed to calculate the calorific value of the sample. 12. Measure the time required to reach 60 per cent of the total rise by estimating the temperature at the 60% point and noting the time from the plot. 13. 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 until the rate of the temperature change becomes constant over a period of 5 minutes. 14. After the last temperature reading, stop the motor, remove the belt and lift the cover from the calorimeter. Wipe the stirrer with a clean cloth and set the cover on the A37A support stand. Lift the bomb out of the bucket; remove the ignition leads and wipe the bomb with a clean towel.

15. Open the knurled knob on the bomb head to release the gas pressure before attempting to remove the cap. This release should proceed slowly over a period of not less than one minute to avoid entrainment losses. After all pressure has been released, unscrew the cap; lift the head out of the cylinder and place it in the support stand. 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. 16. 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 10 centimeters and enter this quantity on the data sheet as the net amount of wire burnt, c1. 17. Each group will hand over a thumb drive to the lab officer in charge for downloading of the scanned data from the central computer 18. On completion of the experiments, students are required to wash the bomb set thoroughly with soap and water. Keep the bomb set dry and clean with the provided wiping tissue

CALCULATION OF THE HEAT OF COMBUSTION

Assembly of Data. calorimeter. The following data should be available at the completion of a test in a 1341

a = time of firing b = time (to the nearest 0.1min.) when the temperature reaches 60% of the total rise c = time at the beginning period (after the temperature rise) in which the rate of temperature change has become constant ta = temperature at time of firing, corrected for thermometer scale error tc = temperature at time c, corrected for thermometer scale error r1 = rate (temperature units per minute) at which temperature was rising during the 5-minute period before firing r2 = rate (temperature units per minute) at which temperature was rising during the 5-minute period after time c. If the temperature was falling instead of rising after time c, r2 is negative and the quantity r2(c-b) becomes positive and must be added when computing the corrected temperature rise c1 = centimetres of fuse wire consumed in firing W = energy equivalent of the calorimeter, determined under STANDARDIZATION mf = mass of sample in grams Temperature Rise. equation: Compute the net corrected temperature rise t, by substituting in the following t = tc ta r1(b-a) r2(c-b) (7)

Gross Heat of Combustion. Compute the gross heat of combustion, Hg, in calories per gram by substituting in the following equation:
Hg tW e1 mf

(8)

where e1 = correction in calories for heat of combustion of fuse wire

= (2.3) (c1) when using Parr 45C10 nickel-chromium fuse wire

CALCULATION/ RESULTS & DISCUSSION

1) The point of transition from the period of heat gain to the period of heat loss occurs at the time when the temperature rise has reached 60% of its total amount. You must estimate this time as accurately as possible. Plot carefully the Temperature (oC) vs. Time (minutes) curve of the calorimetric process, present a record of all necessary data and calculate the gross calorific value of the fuel sample. Discuss the implications of (a) a low oxygen charging pressure (below 30 atm.), (b) excessive fuel sample, and (c) if the bomb was pressurized with air at 30 atm. For very high precision work, discuss the major corrections that have to be applied to the calorimetric procedure and included in the calculation of the calorific value.

2) 3)*

* for formal report only

REFERENCES
1) 2) 3) 4) Frenkel, M., Thermochemistry and Equilibria of Organic Compounds, VCH Publishers, Inc., 1993. Daniels, Williams, Bender, Alberty, Cornwell, and Harriman, Experimental Physical Chemistry, 7th edition, McGraw-Hill, 1970, Chapter 2. Shoemaker, Garland, and Nibler, Experiments in Physical Chemistry, 6th edition, McGrawHill, 1996, Chapter 6. Parr Instrument Company, Instructions For The 1341 Plain Jacket Oxygen Bomb Calorimeter, Technical Manual, 1982.

Figure 1.

The oxygen bomb calorimeter.

Figure 2.

Tying of fuse wire loop. 6

Figure 3.

Typical temperature time curve of a bomb calorimetric process.