Experiment P2: Bomb Calorimetry

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1. Motivation The heat released by a reaction is identical to the enthalpy change of that reaction if the reaction takes place at constant pressure. Measuring and predicting the enthalpy change in a reaction is essential to our understanding of chemistry. It is through the measurement of enthalpy that we know about the strength of different chemical bonds, the extra stability or aromatic molecules, the ring strain in cyclic compounds. Most of the ideas of greater and lower stability of molecules in chemistry has been investigated in the early times using thermodynamic methods. In this experiment we use an experimental set up known as bomb calorimeter to measure the heat generated by a combustion reaction. Calorimetry is still used in many areas of modern science. A similar experimental set up is used currently in food chemistry to measure the calories associated with different foods and to study the properties of fuels. More sophisticated instruments, available in our research labs, can be used to measure very small enthalpies, for example the enthalpy of binding between biological molecules and materials. 2. The idea The heat released in a reaction causes an increase in temperature in the surrounding. To measure the heat we can then let the reaction take place in a sealed container surrounded by a precise amount of water (the calorimeter) and measure the increase of temperature of the water. The relation between released heat Q and temperature increase T is

Q T Ccal
where Ccal is the heat capacity of the calorimeter, which, in general, is also not known. So, the first step is to measure the increase of temperature T for a reaction for which the heat released Q is known: this will allow the computation of Ccal . This step is known as the calibration of the calorimeter. Then we can measure the increase of temperature T for a reaction with unknown heat released and, since we have computed Ccal we can determine Q for the reaction. In this experiment we calibrate the calorimeter using the combustion reaction of benzoic acid. We then measure the heat generated by the combustion of a candy (made mostly by sucrose). 3. The actual instrument The reactions take place in a bomb, a metallic container that will hold the sample in an atmosphere of high pressure oxygen, which will facilitate complete combustion (see figure 1). As you expect, a thermometer (digital in our case) monitors the temperature of water. To make sure the combustion happens when it is desired, fuse wires are included in the bomb and connected to an ignition mechanism that allows the bomb to be fired. A stirrer allows the heat to be more evenly distributed in the water. The actual experimental set up creates two additional complications to our simple initial analysis.

First, the fuse wire will generate a bit of heat. So that the equation relating the Q of the reaction with the increase of temperature should be modified by the amount of heat generates by the fuse wire e f .

Q e f T Ccal
e f can be determined from the amount of fuse that has burned (see detail below).
A second complication is that the calorimeter can itself exchange energy with the environment. The stirrer will cause a slight constant increase in the temperature of water before the reaction is initiated as the mechanical work is transformed into heat (incidentally this is Joules observation that led to the formulation of the first principle of thermodynamics). Moreover, a few minutes after the combustion has taken place, the temperature of water may be still increasing because of the stirrer or it may decrease because the slightly warmer calorimeter is releasing heat to the surrounding environment. A typical profile of temperature versus time is in figure 2 (see section 5). For this reason the quantity T , that goes in the formula above, cannot just be the increase of temperature before and after the reaction (this value keeps changing with time), but it is evaluated via a simple procedure using the data points in a graph of temperature versus time (described in section 5). Figure 1

3. Relation between heat generated Q and the thermodynamic functions U and H The reaction in the container has taken place at constant volume, not pressure. According to the first principle of thermodynamics, considering that the container cannot do any work at fixed volume, the measured heat is equivalent to the change of internal energy U and not the change in enthalpy H . However, the relation between enthalpy and free energy is

H U pV
The variation of the product pV (pressure times volume) at a given absolute temperature T can be computed using the law of gasses if we know the stoichiometry of the reaction. In fact pV nRT ( n is the number of moles of gas and R the gas constant) and pV n RT , where n is the variation in the number of moles between gaseous reactants and gaseous products. It is assumed that the volume of the solid reactant is so small compared with that of the gas that it can be ignored. In summary, the heat measured by the calorimeter is U of the reaction happening inside the bomb, but the enthalpy of the reaction can be also computed via H U n RT .

Pre-lab questions 1. Find the formula of benzoic acid (if not known) and express the balanced chemical reaction of combustion for this compound. Find out what the meaning of combustion is, in case it is not known. 2. What is the difference between enthalpy change ( H ) and internal energy change ( U ) when 1.00 g of this compound is combusted at 300 K. 3. The heat capacity of 1 g of water at 14 C is 1.00 cal C-1. How many calories are needed to warm up a litre of water by 3 C. 4. Express the relation between the units cal, Cal and kcal. 5. Discuss briefly (less than 50 words) the possible risks associated with this experiment

5. Schedule of the experiment and samples to be considered Divide yourself into two sub-groups. Each sub-group will perform two runs of the experiment. Each of the four runs will analyse a different sample: Run 1: benzoic acid in preformed pellets (available in a blue bottle). Run 2: sucrose (table sugar) pellet to be formed using the press Run 3: a candy (defined as Candy A) provided or brought in the lab by you Run 4: another candy as above (defined as Candy B) The initial set up in the schedule to the right consists into taking what is needed from the drawer and performing step 1 of the procedure. All other steps need to be performed each time. The clear up step consists into leaving everything as it was found and where it was found. The extra time needed by sub-group 1 to do this operation is compensated by the fact that sub-group 2 has to prepare a pellet sample (the instructions for that are given separately in a laminate). The detail of the data analysis required is given in section 7. Additional questions to be answered in your report and not requiring the data are in section 8. Note that the results of both groups are needed for the lab report so you need to plan an efficient way to exchange data before the lab is finished. The timing is only to give an idea.

5. Procedure (see also pictures at the end of these instructions) The procedure is identical for calibration with benzoic acid pellets and measurements of new samples (sucrose or candies) and so it is reported only once. Preliminary Bomb Preparation 1. Install the thermistor by sliding it through the opening of the calorimeter cover. Adjust the length of the thermistor to match the length of the stirring shaft. Tighten by hand, the nut to secure the thermistor. 3

2. Weigh out a sample of benzoic acid or other substance. The sample size must not exceed 1.1 g. Larger samples would evolve more than the calorimeter maximum of 10,000 cal and might cause an explosion. 3. If your sample is a powder (not liquid or a compact solid), form the sample into a pellet using the press provided. 4. Attach a measured length of fuse wire (about 10 cm, but note the actual length) between the electrodes. Let the wire touch the pellet. 5. Carefully lower the head onto the bomb. Turn the screw cap down hand tight; never use a wrench. 6. With the help of the demonstrator the first time, attach the filling connection from the oxygen tank to the bomb. 7. Close the control valve (black knob) on the tank regulator. 8. Crack open (1/4 turn) the main valve on the oxygen tank. 9. Slowly open tile control valve. Let the bomb pressure increase slowly to 30 atm. Close the control valve. NEVER CHARGE TO MORE THAN 35 ATM. 10. Relieve the pressure in the connecting tube by flipping the relief valve (underneath the control valve). 11. Remove connecting tube from bomb. (The bomb has a one-way filling valve which automatically closes.) 12. Fill a 2-liter volumetric flask with distilled water. This should be 1-2C below room temperature. Pour it into the oval bucket. Place the bucket in the calorimeter. 13. Attach the lifting handle to the two holes on the side of the screw cap and partially lower the bomb in the water (careful not to disturb the sample). Attach the electric cables connected to the ignition unit. 14. Lower the bomb completely. Make sure that the stirrer runs freely and remove lifting handle shaking any water drops back in the bucket. Firing the bomb 15. Close the calorimeter cover. Slip the drive belt onto the pulleys and start the motor. Turn on the digital thermometer. 16. Let the stirrer run for about 3 minutes equilibration (without taking any data). 17. Note the time and record the temperature every minute for 5 minutes. Prepare for what you have to do after 5 minutes. 18. At the start of the 6th minute (t=5:00) stand back from the calorimeter and fire the bomb by pressing the ignition button and holding it down until the indicator light goes out (keep pressing for 4 seconds). Stay away from the calorimeter for 30 seconds. 19. Record the temperature every minute (or every 30 seconds), you will notice a rapid increase (rise period), lasting 3-4 minutes followed by period where the temperature changes very slowly. When the temperature starts changing slowly, also note the rate of the temperature change, i.e. degree change every minutes. 20. The temperature measurements are concluded when the rate of temperature change is constant for 5 minutes. And finally 21. Stop motor, take out belt, place cover on its support, lift the bomb, remove ignition leads, wipe the bomb with a clear towel and minimize splashes. 22. Release the gas pressure from the knurled knob on the bomb head (slowly, in no less than 1 minute). Unscrew the cap, lift the head and place on its support. Examine the interior of the bomb for soot or evidence of incomplete combustion (the experiment needs to be discarded if such evidence is found). 23. Remove all unburned pieces of fuse wire from the bomb electrodes, straighten them and measure their combined length in centimetres. Subtract this length from the original length of the fuse to evaluate the length of fuse that has burned. 4

6. Calculating the heat of combustion The heat of combustion, the increase in temperature, and the heat capacity of the calorimeter are related by

Q T Ccal e f
where e f is the correction in calories for heat of combustion of fuse wire and is given by the length of the burnt wire (in cm) multiplied by the predetermined constant 2.3 cal/cm. How to evaluate T is explained below. The equation above is used to determine Q if Ccal of the calorimeter in known and the property of the sample are unknown. The same (rearranged) equation is used to determine Ccal of the calorimeter when an experiment is run with a reaction that releases a known amount of heat Q in the calibration of the instrument. Standardization is carried out with pellets of benzoic acid, which are known to release 6318 cal/g.

T is approximately the increase of temperature after the ignition. However, as the temperature changes continuously during the experiment we need a standardized procedure to make the measurement more reproducible and to account for the extra heat given by the stirrer and released by the bucket to the environment. The procedure is as follows:
We consider 5 special points in the plot of temperature versus time. As an example consider the data in figure 2. The first four are simple: (i) The point at time t0 =0 min when the experiment begins; (ii) the point at time ta =5 min when the bomb is fired (iii) the point at time td when the experiment was interrupted because for 5 minutes the rate of temperature change was constant (iv) the point tc , five minutes before td . (v) The fifth point is defined at a time tb where 60% of the temperature rise between ta and tb has taken place. A short table can be built with these data points (data are only to provide an example) Data Point 0 a b c d t / min 0 5 6.3 13 18 T / C 24.340 24.420 26.292 27.540 27.515

The standardized temperature variation can be computed from the formula (T T ) (T Tc ) T Tc Ta a 0 (tb ta ) d (tc tb ) (ta t0 ) (td tc ) The heat of combustion should be reported per gram (for complex substances) or per mole (for pure substances). The former is the specific heat of combustion the latter is the molar heat of combustion.

Figure 2. A typical run of the calorimeter. 7. To be included in your report State the subgroup (1 or 2) you have been working in (i) Describe in less than 100 words the scope of each of the four runs. (ii) Report all the data needed for the computation of the heat capacity or the heat of combustion with appropriate error (for each run). A table like the one below can be useful and compact (not compulsory). The error of each measurement should be estimated. (iii) Report the detail of the calculations made to compute heat capacity or heat of combustion, including error propagation (all runs). (iv) Report the plot of temperature versus time only for the two runs your subgroup has performed and show in the plot the five points used to compute T . (v) For each run report the specific heat of combustion and, when it can be computed, the molar heat of combustion. (vi) Do not report the procedure but you may include important or unusual observations (e.g. incomplete combustion, important data point missing, etc)

Run 1 Sample Type Sample Weight Wire length t0 | T0

Run 2

Run 3

Run 4

ta | Ta tb | Tb

tc | Tc
6

td

| Td

T Q
Ccal Comments

8. Questions to be answered in your report You can search for any data you need to answers these questions on books, web etc Discussion with other students is allowed. 1. A large portion of the calorimeter is constituted by ~2 Kg of water. Can you estimate the approximate heat capacity of the calorimeter? Discuss if the value that you have measured is acceptable. 2. Describe possible sources of systematic errors in the bomb calorimetry experiment. 3. Show that the formula used to compute T becomes simply the difference between the first and last measured point if the temperature is constant before ignition and after the rising period. 4. Describe how the enthalpy (not the internal energy) of combustion of sucrose can be evaluated from the data you have collected (or you will collect). 5. A substance handled in air is easily contaminated. What is the systematic error in computing the molar heat of combustion of sucrose if a sample is contaminated for 0.1% in weight by atmospheric water.

Figure 3. Photographs Illustrating of some steps of the procedure.