Thermodynamics

HEATS OF COMBUSTION AND HEATS OF FORMATION Old Version This experiment will provide experience with experimental heat measurements using a bomb calorimeter to measure the heat of combustion of naphthalene and to determine the heat of formation of naphthalene. METHOD In this experiment, a substance is burned in an excess of oxygen in a stout vessel of constant volume. This "bomb" is immersed in a larger vessel of water. The heat evolved in the bomb is absorbed by the water, resulting in a small temperature rise. From the temperature change and the heat capacity of the system the amount of energy released in the combustion can be measured and the heat of formation calculated. The heat capacity of the system is determined by burning a calibration substance (in this case benzoic acid) of known heat of combustion. EXPERIMENTAL With the equipment provided it should be possible to determine a heat of combustion with an error not to exceed about 0.2%. You may not achieve this accuracy without considerable practice, but you should understand the reasons for the procedure and follow it as closely as practical. Heats of combustion are now frequently determined with much higher precision, but at about the 0.2% error level, several sources of error simultaneously become important and require the application of corrections. In all runs, the charge is to be chosen so as to produce a temperature rise of 2 0.04C. (This can be approximated from the data given at the end of this handout). In all cases, the initial temperature is to be 23 0.02C, and the final temperature 250.02C. The use of the same initial and final temperatures throughout will largely eliminate thermometer errors. Furthermore it practically eliminates errors due to the fact that the combustion is actually not perfectly adiabatic. The possible errors due to heat transfer will be practically the same on all runs and should cancel. If the final temperature closely matches that of the surroundings, there should be virtually no heat leak as this temperature is approached, and there need be no great haste in determining the final temperature. This is true for the above temperatures provided the surroundings are at 25C. If the surroundings are much different from 25C, then you may want to use a starting temperature 2C below the temperature of the surroundings. Consistency is most important in this experiment. If you do your calibration runs from 21 to 23C, then make sure you do your unknown runs over the same range. Before firing the charge, there will be a small temperature drift due to thermal transfer from the warmer surroundings, but it has been shown theoretically that any resulting error is practically eliminated if the effective temperature rise, T2 - T1, is determined as shown in Fig. 1.

Heats of Combustion . . .

Figure 1 Schematic Bomb Calorimeter Time Profile

The energies of isothermal combustion, E, are to be determined relative to a standard substance, benzoic acid, which is very reproducible and has a well known value of E. If the temperature interval could be exactly reproduced, the relative E's (per gram) would be in inverse ratio to the masses required to produce the two degree temperature rise. If this is not strictly achieved, small corrections must obviously be made to your actual measurements. Your first run will be made with benzoic acid, the calibrating substance, in order to become familiar with the procedure and to determine the heat capacity of your system. From the data given at the end of this handout, estimate the mass of reactant required to produce the 2C temperature rise. (For the trial run with an unknown substance, use about 0.5 gm.) Weigh out a quantity in about 5% excess of this amount and compress firmly in the pellet press. The pellet, somewhat larger than a common aspirin tablet, should be neither so soft that it tends to crumble, nor so hard that it may crack in combustion. Also weigh a clean combustion crucible and a 10 cm piece of fuse wire. Bend the fuse wire into a U shape and, using the batteries and clip leads, heat the wire and melt it into the pellet. (You may want to trim the pellet at this point if you think its weight is too high.) Place the pellet and wire in the crucible and weigh. Fit the crucible firmly in the wire holder of the bomb head and attach the ignition fuse wire to the support posts by passing the fuse wire through the hole in the post and sliding the small clamping cylinder down over the fuse wire. Pull as much fuse wire through the hole as you can while leaving the pellet resting on the bottom of the crucible. Make sure the fuse wire is not touching the edge of the crucible.

Heats of Combustion . . .

In precision work, the fuse is a fine platinum wire which may melt, but will not be consumed. In common work, it will be a nichrome wire which will be partially oxidized, necessitating a correction for the heat liberated. The energy input due to electrical heating of the wire is not negligible, but should be below your limit of error. Use the test meter to measure the resistance between the bomb terminals; it should be less that 5 ohms. If not, check the attachment of the fuse wire to the supports. During the remainder of the setup procedure, recheck the resistance periodically to make sure that the fuse wire has not been accidentally broken. Before closing the bomb, place 1 ml of distilled water on its floor . The purpose is, first, to saturate the oxygen with water vapor so that all water produced in combustion will condense, and second, to take up any nitric acid, etc. which may be produced if the compound burned contains nitrogen. When closing the bomb, use firm but not excessive pressure when screwing on the collar. Be careful not to damage the threads. Never use excessive force on the threaded fittings; if they leak, they are defective and will not be improved by violence. Ask the instructor to assist you the first time you charge the bomb with oxygen. The bomb should be flushed twice to remove nitrogen and then cautiously filled to 30 atm, not more. Close the filling valve and open the relief valve (the black ball underneath the gauge assembly). This releases the pressure in the filling line allowing a spring loaded, non-return valve in the bomb to close. It also enables you to disconnect the filling line from the bomb. After any filling, and after the combustion, do not attempt to open the bomb until the pressure has been gently released by use of the bleed valve. Meanwhile, 2000 gm of distilled water at the desired starting temperature needs to be placed in the water can. Do the following: place about 2.5 litres of water in a large beaker, and using the heating blade or ice adjust the temperature to about 2.5 Celsius below the desired ending temperature. Use a two litre volumetric flask to measure out 2 litres of this water into the calorimeter bucket. Fill the volumetric to its mark and carefully pour the water into the bucket. The important point is that the same amount be used in all runs (i.e. use the same volumetric in the same way for each run.) After the final pressurization and before submerging the bomb in the water can in the calorimeter it needs to be checked for leakage, as this would damage the bomb when it is fired. Using a squeeze bottle, fill the depression on the top of the closed, pressurized bomb with water. Also place some water in the top of the filling connection and on the top of the relief valve. Look for active bubbles (bubbles that grow and/or rise) for 2-3 minutes. If you see any call the lab coordinator for advice. If no active bubbles are found, mop out the water with a paper towel. Note that the water bucket has a "boss" on the bottom to position the bomb off center in the bucket. The bucket should be positioned in the calorimeter jacket such that this "boss" (and hence the bomb) is toward the front of the jacket. (When the lid is in place the thermometer should be immersed in the narrow space between the bomb and the side of the bucket, and the stirring device in the wide space.) Submerge the bomb using the wire loop with hooked ends that fit into holes in the side of the collar, and again make sure that no oxygen leakage occurs. The will be some
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Heats of Combustion . . .

bubbles from the holes in the collars. This is normal (to release air trapped above the threads in the collar.) Now assemble the apparatus as shown in Figure 2, make and test the electrical connections, and start the stirring motor. The schedule of temperature measurements is shown in Figure 2 The thermal drift should be followed through a sufficient time and temperature interval that it becomes constant, but if possible the fuse should be fired at 2 below the desired final temperature.

Figure 2 Bomb Calorimeter Layout

After a successful firing of the charge, remove the bomb from the apparatus, cautiously release the pressure as described above, and remove the cover. Note any evidences of incomplete combustion. If satisfactory, flush out the 1 ml of water in the base of the bomb and titrate with a dilute base, (only necessary if the compound contains nitrogen) and apply suitable corrections. You should make at least two consistent runs on each compound (two on benzoic acid and two on naphthalene.)

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CALCULATIONS The experiment can be understood in terms of the following diagram:

bomb + reactants + water bath at T 2 III

bomb + products + water bath at T 2 II

I bomb + reactants + water bath at T 1

Since the process is carried out at constant volume, the function E will be used. The object of this experiment is to find EIII. The process that is actually carried out is Step II for which E=0. The quantity EI is readily calculated if the heat capacity of the system, C, is known. Thus, EIII = C(T2 - T1) + 0 (1)

since E is independent of the path. In this experiment C is evaluated by running the combustion on a substance for which EIII is known and reproducible. The substance used for this calibration purpose is benzoic acid. It is customary to tabulate the result of the experiment not as E, but as -H, the heat which would be liberated if the combustion took place isothermally and at constant pressure. To do this, one uses the relationship HIII = EIII + nRT2 (2)

where n is the change in the number of moles of gaseous contents of the bomb occuring in the combustion. A second method of tabulating the data is to use the standard enthalpy of formation, Hof.

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USEFUL DATA AND INFORMATION: Read the Parr manual sections on Hazards of Operation . Approx. heat capacity of the system (including bomb, bucket, and 2 litres of water) = 2422 cal/deg Approx. internal volume of the bomb = 362 ml Approx. thermal drift to be expected at 23C = 0.002\C per minute per degree difference in temperature from surroundings. Standard Molal Heats of formation from the elementary substances: Substance Hof| (cal/mole at 25C) CO2 (g) H2O (l) HNO3 (in dilute aqueous soln.) -94,052 -68,317 -13,800

E for the constant volume combustion of benzoic acid under the conditions of this experiment: 6,317.8 cal/gm REFERENCES 1. Richard M. Badger, Experiments in Physical Chemistry, California Institute of Technology (1961) p. A1 ff. 2. National Bureau of Standards Circular C461 "Selected Values of Properties of Hydrocarbons," (1947). 3. Handbook of Chemistry, N. A. Lange, editor, McGraw-Hill Book Co. 4. Experiments in Physical Chemistry, Shoemaker, D. P., Garland, C. W., Steinfeld, J. I., and Nibler, J. W., 4th Edition, 1981, pp. 125-139.