Chemistry 472

Fall 2000

Bomb Calorimetry
Introduction In this experiment you will use a Parr bomb calorimeter to determine the heat of combustion of naphthalene. Additional, you will determine the caloric content of a foodstuff such as bread or chips. Useful references for this experiment are the Thermochemistry chapter in Experiments in Physical Chemistry by Shoemaker, Garland, and Nibler; the Parr calorimeter manuals; and your physical chemistry textbook. Experimental Apparatus Heats of combustion of solids and liquids can be determined using a bomb calorimeter. For solids, the substance is pressed into a pellet, attached to a fuse wire and placed inside the bomb. The bomb is then charged with oxygen to a high pressure (20 - 30 atm) and immersed in water in the calorimeter bucket. The reaction is initiated by passing a current through the fuse wire. The heat of combustion is determined from the rise in the temperature of the calorimeter when the combustion reaction takes place. In order to make this determination the effective heat capacity of calorimeter must first be measured by analysis of a standard material such as benzoic acid. Additionally, corrections for the combustion of the fuse wire, formation of nitric acid, exchange of heat between the calorimeter and its surroundings, and mechanical energy added to the system by the stirrer must be applied if an accurate measurement of the heat of combustion is to be made. Procedure You will analyze at least two samples of benzoic acid in order to determine the effective heat capacity of the calorimeter. Then the heat of combustion of naphthalene will be determined by analyzing two samples. The following instructions should be used for all analyses. More detailed instructions are contained in Instruction Sheet No. 204M and No. 205M from the Parr Instrument Company. Obtain copies of these from your TA. 1. Prepare the sample. Weigh out approximately 0.5 to 0.95 g of the sample. Grind the sample to a fine powder with a mortar and pestle (not necessary for benzoic acid). Using the pellet press, form a pellet of the sample. Clean a sample holder and determine the mass of the pellet by weighing the sample holder with and without the pellet using an analytical balance in room 24. Support the top of the bomb on the stand provided. Cut a 10 cm length of fuse wire (measure its length accurately) and attach the ends of the wire to the electrodes. Insert the sample holder containing the sample and bend the fuse wire down to touch the sample. Fuse the wire to the pellet by briefly connecting the wires to a lantern battery. Do not allow the wire to touch the sample holder. Pipet 1 mL of distilled water into the bomb. 2. Charge the oxygen bomb. The bomb can be dangerous if it is not assembled properly so follow the directions carefully and check all o-rings for nicks. Put the cover on the bomb and screw the cap down tightly by hand. Set the bomb in the bench socket. Attach the filling connection from the oxygen cylinder to the top of the bomb. Take care to align the connection properly before tightening the nut (have your TA check it the first time).

With the valve knob, needle valve, and relief valve closed, open the oxygen cylinder. Then, purge the bomb with oxygen to displace the air from the bomb as follows: IMPORTANT: Let gases into and out of the bomb slowly to avoid popping the pellet out of the sample holder. (a) Slowly open the needle valve until 20 atm of oxygen have been admitted to the bomb, then close it. (b) Slowly open the valve knob on top of the bomb and allow the gas to leak out, then close it. Fill the bomb with 20 atm of oxygen and place it in the metal bucket. 3. Calorimeter assembly. Measure out 2000 mL of distilled water in the 2-L volumetric flask provided. The temperature of the water should be slightly below room temperature. Place the bucket in position in the bottom of the jacket and set the bomb on the raised ring in the bucket. Attach the banana clips to the terminals on the bomb, making sure that the clips do not short to the bomb lid. Add the water carefully to the bucket to avoid splashing. Look for bubbles. If the bomb is leaking, youll need to start over. Place the cover on the jacket with the thermometer at the front, attach the pulley belt, and start the motor. 4. Analysis run. Let the stirrer run for at least two minutes before starting temperature measurements. Record the temperature and time at one minute intervals until a constant drift rate (temperature change with time) is observed for at least five minutes. Estimate temperatures to thousandths of a degree if possible. Tap the thermometer gently before each reading. While standing away from the calorimeter, press the ignition switch and record the time. Do not hold it down for more than 3 seconds. Stay away from the calorimeter for ~30 sec. A sharp temperature rise is expected within this time interval. If this does not happen, a poor connection is indicated. Continue recording the temperature every 15 sec for 4 5 minutes. The temperature will rise rapidly at first and then level off. When this happens begin recording the temperature at one minute intervals. Discontinue temperature measurements only after a slow and constant temperature change has been recorded for at least 5 minutes. 5. Disassembly of the calorimeter. Turn off the stirrer motor, remove the pulley belt and thermometer, and lift off the cover of the jacket. Remove the clips from the terminals and lift the bomb out of the bucket. Open the valve knob on the bomb to SLOWLY release the gas pressure. Unscrew the cap, lift out the head and place it on the support stand. Look for evidence of incomplete combustion if present, the run will have to be discarded. 6. Important final steps. (1) Collect all unburned pieces of fuse wire from the bomb electrodes. Straighten them and measure their combined length in centimeters. Subtract this length from 10 cm to determine the amount of wire actually burned. (2) Wash all interior surfaces of the bomb with a jet of distilled water and collect the washings in a beaker. The bomb washings will contain any nitric acid produced in the bomb. Add a few drops of methyl orange indicator. If the indicator is pale yellow, no acid correction is necessary. Otherwise, titrate the bomb washings with a standard sodium carbonate solution. A 0.0709 N sodium carbonate solution can be prepared by dissolving 3.76 g of sodium carbonate and diluting to one liter with distilled water. Calculations 1. For each run, plot temperature vs. time. Using these graphs, determine the net temperature rise t from the following equation: (1) t = t c ta r1 ( a b) r2 (c b)

where, r1 and r2 are the initial and final temperature drift rates (C/min), respectively; time a is the time of ignition; ta is the temperature of the calorimeter when the sample is ignited; time b corresponds to the time when 60% of the rise in temperature has occurred; time c occurs when the temperature begins to decrease steadily after the reaction; and tc is the temperature at time c. Use the graphs to determine these values for each run. 2. Determine the heat of combustion at constant volume, -U (cal/g) for each sample of naphthalene from:

U =

tW e1 e2 m

(2)

where, W is the heat capacity of the calorimeter (cal/C) determined from the combustion of benzoic acid (see below); e1 is the correction for the heat from the formation of nitric acid (cal), e2 is the correction for the heat from the combustion of the wire (cal), and m is the mass of the sample (g). The heat of combustion of the fuse wire is given on its package. 3. Calculate an average value for U and convert it to units of kcal/mol using the molecular weight of naphthalene. From this determine H (kcal/mol) for the combustion of naphthalene using this relationship:

H = U + RTn g

(3)

where, R is the ideal gas constant, T is the temperature, and ng is the change in the number of moles of gas in the combustion reaction per mole of naphthalene. The heat of combustion is -H for the combustion reaction. 4. Determine the enthalpy of combustion of the foodstuff (kcal/g). 5. Perform an error analysis and estimate the error in your measurement of the enthalpy of combustion of naphthalene and of the foodstuff. Determination of the energy equivalence factor W of the calorimeter. This value represents the effective heat capacity of the calorimeter, has units of cal/C, and is determined from the analysis of benzoic acid. As in the analysis of naphthalene, use equation (1) to determine t for each sample. Then rearrange equation (2) and solve for W assuming that U for benzoic acid is -6318 cal/g. Report the individual and average values for W. Use the average value of W in equation (2) when determining heats of combustion with the calorimeter. Questions Write balanced chemical reactions for the complete combustion of benzoic acid and naphthalene. Approximately how many moles of excess oxygen are present in this experiment? Use the ideal gas law and assume that the bomb has a volume of 350 mL. Is it valid to use the ideal gas law for this calculation? Why or why not? Why is it potentially necessary to correct for the formation of nitric acid in the bomb? What is the source of the nitrogen and how might it be minimized?

Discuss the uncertainty introduced by a lack of knowledge of the specific heat of a sample. What assumptions are made in the derivation of equation (3)? How do the errors introduced by this assumption compare to the uncertainties inherent in the measurements in this experiment? Compare the enthalpy of combustion of naphthalene with the accepted value in the literature (cite your reference). If you have done the experiment carefully, your value should be within 3% of the literature value. Does the H calculated for naphthalene in this experiment pertain to the initial or final temperature? Comment on the results of the analysis of the foodstuff. Is your result consistent with the caloric content reported by the manufacturer? If not, why not?