Jane H. OConnor Biophysical Chemistry Professor: Dr. Yang Yang Lab Partners: Michael A.

Corsello Sunhee Kwon

Experiment 1

Bomb Calorimetry
Strain Energy of Cyclopropane: Experimental and Computational Investigation

Abstract The reason for this experiment was to find the strain energy of cyclopropane with bomb calorimetry techniques. A bomb calorimeter is used to measure the energy transfer of heat as the temperature is changed due to a combustible reaction. The combustible chemicals that were used in this experiment were benzoic acid, 1, 4 cyclohexane dicarboxylic acid and cyclopropane carboxylic acid. The temperature change of benzoic acid was very important since it was used to calculate the heat capacity of the calorimeter, which was ultimately used to calculate the remaining formulas that would lead to the finding of the strain energy. With this value the molar energy of combustion was calculated with the temperature changes of 1, 4 cyclohexane dicarboxylic acid and cyclopropane carboxylic acid. Next, the molar enthalpy change of combustion was found with the molar energy of combustion. Lastly, the strain energy was found with the molar enthalpy change of combustion. The strain energy value that was found for cyclopropane was 121.7 +/- 15.2 kJ mol-1. The literature values for cyclopropane where 120.918 kJ mol-1 from one source and 131.5 kJ mol-1 from another source. The experimental value obtained is found to be within this range which concludes that the experiment conducted was very accurate to literature values.

Introduction Chemical reactions are one of the most important concepts in chemistry. Almost everything in chemistry deals with two subjects reacting with one another. During chemical reactions there is always a heat transfer. This heat transfer is always either endothermic or exothermic. Endothermic reactions consume and take in heat from the surroundings to drive the reaction. Exothermic reactions, on the other hand, produces heat from the reaction and release it into the surroundings. Measuring the heat change in these reactions is very crucial in determining certain properties of the reactants. A property that can be determined through the temperature change of a reaction is the strain energy of a compound. Strain energy is the stableness of a compound and usually causes a compound to be less stable because the geometric structure of the compound causes it to bend and stretch [1]. However, some chemical reactions produce very small temperature changes and are very hard to measure. A device that can be used to determine small temperature changes is a bomb calorimeter. A bomb calorimeter is a device that measures the heat change of a combustible solution. The apparatus contains a bomb which consists of subparts. It contains a bomb head, a shell and a screw cap. The combustible solution is placed inside of a capsule that is attached to the bomb head with two electrodes [2]. A specific length wire is attached to the two electrodes and is made to touch the combustible solution. A small amount of distilled water is placed inside of the bomb shell. The bomb is placed inside of the shell and sealed with the screw cap. Next, the bomb is purged once with oxygen and then filled again with oxygen to thirty-five atmospheres. The bomb is placed in a container that is filled with water that is already inside of the calorimeter. Next, the ignition unit is attached to the bomb and the calorimeter is closed off by placing the cover on the device, which also contains a stirrer. The thermometer is then inserted into the opening at the top of the calorimeter. Afterwards, the stirrer can be attached to the motor where it is turned on. The calorimeter is allowed to equilibriate for approximately five minutes. After this period of time, the bomb is ignited with the ignition unit. There should be a temperature change due to the reaction and again this will be allowed to come to equilibrium. When the bomb is ignited, the combustible solution combusts and the heat produced in the bomb is transferred to the water bath that the bomb is submerged in where it is measured with the thermometer. Throughout the whole process, the reaction is monitored from beginning to end with a computer. The computer produces a graph where it can be analyzed to show a temperature change. For the experiment being conducted, the combustible chemicals that will be used are benzoic acid, 1, 4 cyclohexane dicarboxylic acid and cyclopropane carboxylic acid. Each of these
[1] Garland; Nibler; Shoemaker. Experiments in Physical Chemistry. Vol. 7 pg. 159 [2] 1108 Oxygen Combustion Bomb Operating Instructions, Parr Instrument Company, 211 Fifty-Third St., Moline, IL 61265.

chemicals will be used as a combustible solution in the bomb calorimeter to show a temperature change. The purpose of this experiment is to calculate the strain energy of cyclopropane with bomb calorimetry techniques and to compare them to literature values of cyclobutane. To calculate the strain energy of cyclopropane, the temperature change of benzoic acid, 1, 4 cyclohexane dicarboxylic acid and cyclopropane carboxylic acid will have to be observed with the bomb calorimeter. The benzoic acid is used as a standardization and will be used to calculate the heat capacity of the calorimeter with the following equation:
C ( s) 26.41m BA 6.68m Fe kJ K-1 T

(1)

The symbol m BA represents the mass of benzoic acid used and the symbol m Fe represents the mass of wire burned in the reaction [1]. T is the temperature change of the reaction in the bomb calorimeter. Once the heat capacity for the calorimeter is found, the molar energy of combustion for 1, 4 cyclohexane dicarboxylic acid and cyclopropane carboxylic acid can be found with the following equation:
Ec
~

M [C ( s)T 6.68mFe ] m

kJ mol-1

(2)

The M represents the molar mass of the chemical used in the calorimeter and the symbol m is the mass of the chemical used inside of the bomb [1]. Once that is calculated, the molar enthalpy change can be found with the following equation:

H c E c RT n gas

(3)

The symbol R is the gas constant and the T is the temperature at standard conditions which is
~

298.15 Kelvins. n gas is the number of moles from the gases obtained through the balanced combustion equation of the chemical used [1]. When the molar enthalpy change is calculated, the strain energy is calculated with the following equation:

S ( I ) H c(1,4cyclo) H c(cyclo)
~

(4)

The symbol H c(1,4cyclo) is the H c calculated for 1, 4 cyclohexane dicarboxylic acid and

H c(cyclo) is the H c calculated fro cyclopropane carboxylic acid. When the two H c are subtracted from one another the strain energy is found.

The hypothesis for this experiment is that all of the reactions will be exothermic because when a bomb explodes, heat is always released. Also, the strain energy of cyclopropane will be higher than the literature value for cyclobutane because cyclopropane is more crowded than cyclobutane. Due to this, there should be more bends and stress on the cyclopropane molecule which should lead to a higher strain energy. Since two trials are conducted for each substance, not every two values will be the same. Error analysis should be calculated by finding the mean of the two values and calculating the standard deviation, relative standard deviation, confidence interval and propagation of error. This should eliminate as much error as possible. Experimental The chemical used in this experiment were benzoic acid that was supplied from the Parr instrumental company, 99% 1, 4 cyclohexane dicarboxylic acid, manufactured by Aldrich and 95% cyclopropane carboxylic acid, also manufactured by Aldrich. Benzoic acid has a molecular weight of 122.12 g/mol and is the simplest aromatic carboxylic acid [3]. Both 1, 4 cyclohexane carboxylic acid and cyclopropane carboxylic acid has the same empirical formula but the molecular formula are different because 1, 4 cyclohexane dicarboxylic acid is twice the molecular weight of cyclopropane carboxylic acid [4]. The fuse wire used to ignite the bomb is the type 45C10 fuse wire supplied from the Parr instrument company. Also, a pressurized container supplied the pure oxygen used in the experiment. A model 2811 pellet press was used to make the pellets from the powdered chemicals. The bomb calorimeter used was a model 1341 oxygen bomb calorimeter made form the Parr instrument company which also contained a model 2901 ignition unit made from that same company [5]. The bomb itself was a model 1108 oxygen combustion bomb which contained three sections. It contained a shell, a bomb head and a screw cap. As seen in Figure 1, the combustible sample was placed inside of the capsule, which was attached to the bomb head. The bomb head would be lowered into the shell where it was screwed shut.

[3] Safty Emporium, MSDS for Benzoic Acid, 2004. [4] Chen, F., University of Wisconsin, Strain Energy of Organic Compounds-Bomb Calorimetry. [5] 1341 Oxygen Bomb Calorimter Operating Instructions, Parr Instrument Company, 211 Fifty-Third St., Moline, IL 61265.

Figure 1. Diagram that shows the main components of the oxygen combustion bomb

Once the bomb was assembled, it can be placed in the bomb calorimeter. As seen in Figure 2, the bomb was placed inside of a container filled with water. That entire assembly was placed inside of the calorimeter and hooked to the ignition unit. The calorimeter cap would be placed on the calorimeter and the thermometer was inserted. The stirrer was then hooked to the motor and everything was attached to the transmitter which was attached to the laptop. The transmitter was a LabPro Vernier model.

Figure 2. Diagram shows the entire bomb calorimeter in use with all components in place.

The procedures of this experiment were simple once it was started. First, the bomb calorimeter had to be hooked up to the transmitter and laptop. Once everything was hooked up, the

computer program that collected the data was turned on. After the machinery was set up, the actual experiment was allowed to proceed. The standardization run had to be completed first. A pre-made benzoic acid pellet was weighed out and transferred onto the capsule. The capsule was placed onto the electrode wire that was attached to the bomb head. A piece of fuse wire was cut to about 8.0 cm in length and was attached to the electrodes that were on the bomb head. The fuse wire was made to touch the benzoic acid that was found inside of the capsule. Next, about 1mL of distilled water was transferred into the bomb shell. Afterwards, the bomb head assembly with the capsule, benzoic acid and fuse wire was placed inside of the bomb shell. The screw cap was used next to seal the bomb shut. Compressed oxygen was then transferred into the bomb through an opening at the top of the bomb. It was then purged out to purify the bomb and was then filled once again with oxygen to about 35 atmospheres. Next, the silver container was placed into the bomb calorimeter and two liters of water was transferred into it. The bomb was then carefully transferred and held above the calorimeter where the two electrodes were attached to the ignition assembly. Once attached, the bomb was placed inside of the container with the two liters of water where it was submerged. The bomb was placed inside of the calorimeter so that it was not touching any of the walls. The calorimeter lid was then placed on the machine. The thermometer was then inserted into the opening at the top of the calorimeter lid and the stirrer was attached to the motor. The motor was turned on and the collect button was clicked in the computer program and the system was allowed to equilibriate. Once there was a clear equilibrium line, the bomb was ignited and again the system was allowed to equilibriate. Once the equilibrium was achieved, the stop button in the computer program was clicked and the motor was shut off. Everything was taken out of the calorimeter and cleaned. The bomb was purged to get the oxygen out of the interior and the wire remaining on the electrode was collected and measured. After this run was completed another benzoic acid run was completed with another pre-made pellet. 1, 4 cyclohexane dicarboxylic acid was a powder so it was made into a pellet using the pellet press. Two trials of 1, 4 cyclohexane dicarboxylic acid was ran just like before with the benzoic acid trials after each pellet was made a weighed. The same was done with cyclopropane carboxylic acid. However, this chemical was a liquid and so about 0.8 grams of the liquid chemical was weighed and transferred into the capsule where the procedures of the benzoic acid were followed. Results and Discussion As seen in Table 1 below the materials used in each trial were not the same as another trial so the results obtained should not be the same as another. The benzoic acid pellets were pre-made so the mass of the pellets used were slightly different. The 1, 4 cyclohexane dicarboxylic acid pellets were made with the pellet press and during the pellet formation, some of the powder used

did not make it into the pellet which is the reason for the masses being so different. The mass of the cyclopropane was weighed out in a balance because the chemical was in a liquid form.
Table 1. Initial products used in the experiment and wire length remaining after the experiment.

Trial Benzoic Acid-1 Benzoic Acid-2 1,4 Cyclohexane Dicarboxylic Acid-1 1,4 Cyclohexane Dicarboxylic Acid-2 Cyclopropane Carboxylic Acid-1 Cyclopropane Carboxylic Acid-2

Mass Used (g) 1.0095 1.0050 0.4994 0.5712 0.8460 0.8532

Length Wire (cm) 8.00 8.00 8.00 8.00 10.00 10.00

Remaining Wire (cm) 0.65 2.00 1.40 1.50 1.00 1.90

Before the experiment began a certain length of wire was used as the ignition source. It was placed on the electrode and touched the combustible chemical. When the ignition button was detonated, an electrical current was passed through the wire and caused the chemical to combust. When this occurred the majority of the wire was burned but some of the wire remained. The mass of the burned wire is needed in the calculations of the heat capacity and the molar energy of combustion. The mass of 1cm of wire was found to be 0.00182 grams and with this the mass of the burned wire can be calculated by subtracting the length wire, in the table above, with the remaining wire and multiplying it by 0.00182g. Also shown in Table 1 are two of each species. There were two of each species because two trials were conducted for each chemical. With two trials allows for more data which can show if one run was good or bad by showing if a run deviated from the other. If the two runs deviate too much from one another, then another trial should be conducted to throw out the bad trial.
28.5 28 27.5 27 26.5

Temperature ( C)

26 25.5 25 24.5 24 23.5 23 22.5 22 0 2 4 6 8 10 12 14 16

Benzoic Acid Trial 1 Benzoic Acid Trial 2

Time (min)

Figure 3. Graph of the temperature change of Benzoic acid for two trials. With this change in temperature the heat capacity value can be calculated.

Finding the temperature change of benzoic acid is very crucial in determining the values of the rest of the calculations. It is used to calculate the heat capacity which will then be used to find the molar energy of combustion of the other two chemicals used in this experiment. The molar energy of combustion will then be used to calculate the molar enthalpy change of combustion for those two chemicals which will ultimately be used to find the strain energy of cyclopropane. Figure 3 shown above is the temperature change of benzoic acid as it is ignited in the bomb calorimeter. It is clearly seen from the figure that the reaction was exothermic because there was a positive change of temperature. Each trial was allowed to equilibraite for about six minutes, as seen in Figure 3, before the fuse was ignited. After that, there was a drastic increase in temperature, even though it was a small change, and then it was allowed to settle down once more. Each run lasted for about fifteen minutes. Figure 4 below shows a detailed description on how the change in temperature was calculated for each benzoic acid trials. This method was also used to calculate the change in temperature for 1, 4 cyclohexane dicarboxylic acid and cyclopropane carboxylic acid trials.

Figure 4. Diagram of Benzoic Acid trial 1 depicting the process involved on how to calculate the change in temperature for the reaction.

Each run contained three parts to it, as seen in Figure 4. There was a pre-reaction baseline, a temperature change and a post-reaction baseline. Calculating the change in temperature was a simple task but was the most important calculation of the experiment because every other calculation depended on it. To calculate the temperature change a horizontal line was drawn from the post-reaction baseline to the y-axis and another horizontal line was drawn from the prereaction baseline to the y-axis. This should give two temperatures, Temp H and Temp L. Temp L from the pre-reaction baseline was subtracted from Temp H from the post-reaction baseline to receive the change in temperature. Once the change in temperature was found for the benzoic acid trials the heat capacity of the calorimeter system could be calculated. Using Equation 1 expressed above and the data in Table 1 and with the change in temperature of benzoic acid, the heat capacity was calculated to be 10.4599 kJ K-1 for trial 1 and 10.4262 kJ K-1 for trial 2. The average of the two trials was found to be 10.4431 kJ K-1which would be used for the remaining calculations. Before the remaining calculations can be solved, the change in temperature was found for 1, 4 cyclohexane dicarboxylic acid and cyclopropane carboxylic acid.
29 28.5 28 1,4 Cyclohexane Dicarboxylic Acid Trial 1 1,4 Cyclohexane Dicarboxylic Acid Trial 2 Cyclopropane Carboxylic Acid Trial 1 Cyclohexane Dicarboxylic Acid Trial 2

Temperature ( C)

27.5 27 26.5 26 25.5 25 0 5 Time (min) 10 15

Figure 5. The graph depicts changes in temperature for 1, 4 Cyclohexane Dicarboxylic acid and Cyclopropane Carboxylic acid trials.

The change in temperature for these two chemicals were found in the same manner as the change in temperature of benzoic acid was found. The temperature change for the 1, 4 cyclohexane

dicarboxylic acid trials were 1.0536 C for trial 1 and 1.1833 C for trial 2. The temperature change for cyclopropane carboxylic acid trials were 1.8345C for trial 1 and 1.8285C for trial 2. With this information the molar energy of combustion was calculated with Equation 2 from above and from data from Table 1. With all of the information plugged into the equation the values of -3765.74 kJ mol-1 and -3701.03 kJ mol-1 were found for 1, 4 cyclohexane dicarboxylic acid and the values -1938.35 kJ mol-1 and -1916.77 kJ mol-1 were obtained for cyclopropane carboxylic acid. Once the molar energy of combustion was obtained, that value would be plugged into Equation 3, previously stated, to find the molar enthalpy change of combustion. After being plugged in and calculated, the values for H c for 1, 4 cyclohexane dicarboxylic acid were found to be -3768.22 kJ mol-1 for trial 1 and -3703.51 kJ mol-1 for trial 2. For cyclopropane carboxylic acid the H c values were found to be -1939.59 kJ mol-1 and -1918.01 kJ mol-1. All of these results are summarized in Table 2 below.
Table 2. Summary of calculated values obtained from the experiment. T is the temperature change found from the graphs, C(s) is the heat capacity of the calorimenter system, Ec is the molar energy of combustion and Hc is the molar enthalpy change of combustion.
~ ~

Trial Benzoic Acid-1 Benzoic Acid-2 1,4 Cyclohexane Dicarboxylic Acid-1 1,4 Cyclohexane Dicarboxylic Acid-2 Cyclopropane Carboxylic Acid-1 Cyclopropane Carboxylic Acid-2

T (C) 2.5574 2.5527 1.0536 1.1833 1.8345 1.8285

C(s) (KJ/K) 10.4599 10.4262 -

Ec (KJ/mol) -3765.74 -3701.03 -1938.35 -1916.77

Hc (KJ/mol) -3768.22 -3703.51 -1939.59 -1918.01

Table 2 above is a summary of all of the calculations that shows the values of temperature change for all species, heat capacity of the calorimeter system with benzoic acid, the molar energy of combustion for both 1, 4 cyclohexane dicarboxylic acid and cyclopropane carboxylic acid and also shows the molar enthalpy change for combustion of 1, 4 cyclohexane dicarboxylic acid and cyclopropane carboxylic acid. Once the H c values were found, the strain energy could now be calculated. Using Equation 4 previously stated, the values of H c can be plugged into the formula to find the strain energy. There was only one slight change to the formula and it was to multiple the H c value of cyclopropane carboxylic acid by 2. This was done because the molecular weight of cyclopropane carboxylic acid was only half of that of 1, 4 cyclohexane dicarboxylic acid. With this minor change the strain energy for the first trial was found to be 110.96 kJ mol-1 and the
~ ~ ~

strain energy for the second trial was found to be 132.51 kJ mol-1. The average of the two trials came out to be 121.735 kJ mol-1 which is found to be the strain energy of cyclopropane. Since there were two trials conducted the standard deviation was found to be 15.2382 kJ mol-1 and the relative standard deviation was found to be 0.125175 kJ mol-1. The confidence interval was found to be 121.735 kJ mol-1 +/- 136.908 with a 95% confidence. This value seemed to be very high so the values for the 90% and 50% confidence intervals were also calculated. At 90% confidence the value was 121.735 kJ mol-1 +/- 68.0336 which was still quite high but the confidence interval at 50% was found to be 121.732 kJ mol-1 +/- 10.775 which seemed to be correct since only two trials were conducted. The propagation of error was found to be 22.5501 kJ mol-1 which seems to be correct with the amount of trials that were conducted. In an experiment conducted by Cremer and Gauss, the strain energy found for cyclopropane was found to be 28.9 kcal mol-1, which converts to 120.918 kJ mol-1 [6]. This is an extremely close value to the results obtained in this experiment which was 121.735 kJ mol-1. This is only a 0.6757% of a difference which makes the results very similar. However, a formula derived from the CRC Hard Book of Chemistry and Physics gave a value of 131.5 kJ mol-1 for cyclopropane [7]. This shows that there was a 7.426% difference from the results obtained from the experiment and the calculated result derived from the CRC book. Going on further with other results obtained from Cremer and Gauss, their results for the strain energy for cyclobutane was found to be 27.3 kcal mol-1 which is converted to 114.223 kJ mol-1 [6]. This result actually did not differ all that much from cyclopropane that was obtained from this experiment. It was assumed that cyclopropane would have a much greater strain energy because the cyclopropane molecule is smaller and should have more steric affects but this experiment and the results from a literature source suggests that the strain energy of cyclopropane is not really that high compared to cyclobutane.

Conclusion The purpose of this experiment was to calculate the strain energy of cyclopropane with bomb calorimetry techniques and to compare them to literature values of cyclobutane. The original hypothesis was that all of the reactions will be exothermic and that the strain energy of cyclopropane will be higher than the literature value for cyclobutane. The strain energy was found to be 121.735 kJ mol-1 for cyclopropane from the experiment conducted. The literature values for cyclopropane were found to be 120.918 kJ mol-1 from one source and 131.5 kJ mol-1 from another source. Both literature values were very close to the experimental value and only
[6] Cremer, D.; Gauss, J., Theoretical Determination of Molecular Structure and Conformation, Journal of American Chemical Society, 108, pg. 7467-7477, 1986. [7] Lide, D. R., CRC Hard Book of Chemistry and Physics, 88 th Ed. Pg. 5-70.

differed by a couple of percent. The hypothesis was found to be correct since all of the reactions were exothermic, as seen in Figures 3 and 5, and the strain energy of cyclopropane was higher than literature values of cyclobutane, even though there was only a small difference. The overall experiment went very well. The strain energy was found for cyclopropane and was compared to literature values. The error calculations were very low which allowed for good results. However, there was one major problem that was found. The entire experiment depended on the temperature changes of each chemical. If there was a slight change in temperature, the results would have drastically been different. Since the temperature change was found by drawing a line to the y-axis and due to some vibrations on the graphs, calculating temperature change may not have been very proficient. The best was done to compensate for this data analysis but a better method should be used to further better this experiment. A method that can be done next time is to watch the computer constantly as the reaction is coming to completion and when there is a constant temperature the run should be stopped immediately before the temperature begins to fall. This should help determine a better and consistent change in temperature. The bomb calorimeter, though, was a great machine for this experiment and only so much can be changed on the device.