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To determine the Cv of the calorimeter by burning a standard substance, benzoic acid THEORY Calorimetry is a process involving the measurement of absorbed or evolved heat during a chemical reaction or simply the quantitative measurement of the flow of heat in a reaction. Heat released in a chemical reaction can be determined experimentally by using an adiabatic calorimeter. The reaction must proceed without any side reactions and sufficiently fast that the heat exchange with the surroundings is negligible. Heats of combustion are most conveniently measured using an adiabatic bomb calorimeter. The heat of combustion is directly related to important quantities such as the internal energy and enthalpy of a chemical reaction. The bomb, used in bomb calorimetry, is a completely sealed and oxygen filled metal container. This is placed in an insulated jacket containing a pail of water and a thermometer -- all combined to form the calorimeter. All the conditions surrounding the bomb and its calorimeter, allow for an adiabatic reaction to take place. 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 like benzoic acid, of known heat of combustion. Benzoic acid undergoes the exothermic reaction: C6H5COOH(s) + 15/2 O2 (g) 7 CO2(g) + 3 H2O(l) Calculations for this kind of system will have more emphasis on the △U value because the reaction is carried out experimentally in a closed, constant-volume apparatus and the experimentally measured quantity is the heat associated with the process. Since △U = qV, a measurement of qV gives △U directly. Measuring the mass of benzoic acid at the start of the experiment, enables the calculation of the number of moles reacted, assuming the reaction goes to completion, and thus leads to the calculation of the molar internal energy of combustion. These values can be turned into enthalpy changes, yielding standard enthalpies of combustion, by the definition of enthalpy: H = U + PV so that △H = △U + △(PV), and, since V is constant and P changes only from a change in the amount of gas in the calorimeter, the equation can be written as △H = △U + △(nRT) = △U + RT(△n) where △n = (# moles of product gases) – (# moles of reactant gases) with the assumption that the reaction is carried out isothermally and that the gases are ideal. In the laboratory, most of the experiments are done adiabatically, and the primary data of any one measurement give the temperature rise of the apparatus that accompanies the combustion.
The sample was pelletized thoroughly before it was obtained from the pelletizer. the change in enthalpy (heat of combustion) may be calculated from the change in internal energy (DU) and the change in the number of moles of gas. Filling of the calorimeter with water . If the compound being burned is known. the difference between DU and DH is often unknown and therefore the results should be reported as DU. Careful handling of the pelletized sample was done using the forceps.It is more convenient to conduct the measurement oh heat of combustion of reactions at constant volume rather than at constant pressure. b. The pelletized sample was then weighed to account the losses during pelletizing.500 mL distilled water– for washing purposes benzoic acid – minimum of 0. The pelletizer was first cleaned to avoid any contamination on the sample.5 g Platinum fuse b. The heat evolved is absorbed by the calorimeter and is equal to the change in internal energy ( △U) rather than the change in enthalpy (△H). PROCEDURE a. The sample mass was also ensured to not exceed 1. Laboratory Equipment bomb calorimeter wire sample pelletizer ruler oxygen tank stopwatch volume measuring equipment ( graduated cylinder/beaker) clean towel long stem thermometer forceps analytical balance cutter/scissor IV. before firing. The weighed sample was then pelletized in the sample pelletizer.5 g of the sample (benzoic acid) placed in an ordinary paper was weighed using an analytical balance.5 g. Preparation of sample( benzoic acid) Approximately 0. The bomb was also checked for any leakage as evident by the formation of gas bubbles at any point on the bomb when it is submerged in water. If the composition of the material is unknown. The laboratory technician made sure that the oxygen pressure did not exceed 590 psig (40 atm). c. MATERIAL AND APPARATUS a. III. PRECAUTIONS Certain precautions were observed while conducting the experiment. Materials and Reagent distilled water – minimum of 3.
The experiment required 3. The Oxygen tank valve was then opened not more than one quarter turn. Closing the bomb The bomb head was carefully moved from the support stand to the bomb cylinder to avoid detachment of sample from the fuse. The filling connection control valve was afterwards opened and the pressure gage was observed to rise to the desired filling pressure of 100-120 psig. Filling the bomb with Oxygen The control valve at the top of the bomb was opened. Then the Oxygen-filled bomb was slowly placed in the center of the bucket-filled with water. The attached fused was bended toward the top surface of the sample and was made sure to firmly settle on it to keep it from sliding against the side of the capsule. The bomb head was then placed into the cylinder and was pushed down as far as possible without twisting it while the gas release valve was open. The group has done certain preparations before obtaining the required water conditions. The whole procedure was done by an authorized laboratory technician who knew the whole process very well. e. and to fix . release the pressure. Pre-firing The two ignition wires were attached to the terminal sockets on the bomb head. The hose from the Oxygen tank was connected to the control valve and was securely tightened.3 °C to be filled in the bucket where the bomb is to be submerged. The steel capsule was first made sure to be thoroughly cleaned. The bomb head was placed on the support stand and the fuse was securely fastened between the two electrodes in the bomb head.000 mL of distilled water with a temperature of approximately 25 ± 0. in conformance to the safety precautions involve in conducting the experiment. The cut wire was then weighed in the analytical balance. h. f. The set-up was then checked for any gas leakage by observing for continuous production of air bubbles. Calculations employing heat balance was done in estimating the volume of water of different known temperatures to be measured. Attaching the Platinum fuse Eight centimeter (8 cm) platinum wire was cut with the use of a ruler and a scissor. g. In closing the bomb properly. Securing of sample in the bomb head The pelletized sample was carefully placed in the steel capsule using the forceps. and it was weighed before the sample was placed in it. d. The temperature of water at room temperature was measured to be higher than 25°C so the group decided to cool some water to lower the temperature to approximately 25°C. For leakages. the screw cap was then set on the cylinder and was firmly turned down until it was very tight. so that the standard heat of reaction can be obtained. it was required to remove the bomb from the water. The control valve was then closed.
The firing button was then pressed for about 1-2 seconds. The interior of the bomb. it is needed to proceed by closing the cover and by seating the cover snugly against the calorimeter. The initial temperature of water was recorded. A second trial was then conducted using the same procedures. Then. It was then brought outside the room. making sure that it reaches the water level in the bucket. Without the observation of leakage. ILLUSTRATION OF SET-UP Figure 1 – Parts and components of a bomb calorimeter. The screw cap was removed and the bomb head was lifted and placed in the support stand. The stirrer was then turned on for 6 minutes. The time after firing at which the first temperature rise occurred was also recorded. The gas that was released was then observed. Firing of the bomb The ignition unit was plugged to the power source and was turned on. i. and the temperature of the water was read every 30 seconds. The capsule was again weighed to account for the materials that were formed in the capsule. The thermometer was then inserted in the cork and was inserted in the hole provided on the cover of the calorimeter. before starting the experiment again. the stirrer was turned off and all electrical connections were unplugged. V. The fuse was also measured afterwards. and the gas release valve was opened gradually to get rid of the residual gas pressure. . Recovery of the combustion products After 18 minutes of observation period. The temperature was recorded every 30 seconds for 12 minutes after firing. the calorimeter cover was opened and the bomb was lifted and was wiped dry. particularly the capsule. before removing the screw cap. was then examined for soot and other evidence of incomplete combustion. j.the leak.
9 210 24.1 480 25 25.4 25.3 25. DATA.35 630 25.9 25.6694 Mass of Pellet (g) 0.9 24.9 24.0129 Measurements after Combustion Mass of Capsule (g) 12.0134 0.5029 0.2 25.5 25.9 24.5 780 25.5 25.9 270 24.9 24.9 24.9 After Firing 390 24.8 24.9 24.9 300 24.9 30 24.0072 0.4 25.9 240 24.2 540 25.9 24.35 600 25.4968 0.9 150 24.0028 Mass of Soot Formed (g) 0.9 24.5 750 25.9 60 24. Initial Measurements: TRIAL 1 TRIAL 2 Mass Benzoic Acid (g) 0.4625 12.9 330 24.4 25.4 720 = T12 25.55 .3 570 25.4 660 25.0101 △m benzoic acid 0.05 450 25 25.9 24.5128 Mass Capsule (g) 12.4553 12.9 24.6795 Mass of fuse (g) 0.4 25.9 120 24.4 690 25.2 510 25 25.9 90 24.4938 Mass Fuse (g) 0.9 25 420 24.9 24.4 25. ANALYSES AND RESULTS Table 1 –Measurements of reagents and materials before and after combustion.9 360 = 6 min= T6 24.VI.9 180 24.5027 Table 2 – Time and temperature measurements before and after firing. Time Temperature (°C) st (seconds) 1 Trial 2nd Trial Stabilization period 0 24.5301 0.9 24.
6 25.810 840 870 900 930 960 990 1020 1050 1080= T18 Trial 1: T0 =24.55 25.2 25.55 25.5 °C T18 = 25.4 25.6 25.6 25.6 25.6 25.1 25 24.6 Trial 2 T0 = 24.6 25. the temperature rises very minimally.6 25.6 25.9 °C T12 = 25. in determining the heat capacity of the calorimeter.8 °C T6 = 24. .9 °C T12 = 25.5 25. Trial 1 25.6 °C tfirst T rise = 40 s 25.6 25.6 25.8 24.6 The experiment used benzoic acid.6 25.6 25.6 25. with a known heat of combustion.6 25. As can be seen on Table 2.6 25.9 °C T6 = 24. The data presented in Tables 1 and 2 are the data necessary in order to calculate for the Cv of the calorimeter.6 25.7 25. These data were obtained from the experiment.4 °C T18 = 25. before and after the combustion process.9 24. and the difference between the final and the initial temperature of water from zero to 18 minutes is a small value.5 Temperature (°C) 25.6 °C tfirst T rise = 25 s 25. Below is a plot of temperature vs time for the two trials.7 0 200 400 600 time (s) 800 1000 1200 Figure 2 .3 25.Plot of temperature vs time for the combustion of Benzoic acid in trial 1.
Soot was found to be deposited in the capsule and such particular observation suggests that the combustion is incomplete. the sample loss incorporated in attaching the fuse to the surface of the sample. The plot represents the manner at which the temperature of the water increased after combustion. Some other unaccounted factors. The disappearance of the fuel in the capsule. errors arise. the inaccuracy in reading the temperature from the thermometer for every time interval can be cited as a human error.1 25 24. The experiment is simple but it has become tedious due to the repetitions done every time mistakes are inevitably done. like the probable contamination in the sample. The temperature can be observed to be constant at some point in the graph.6 25. indicated that combustion had indeed occurred. signifying that the combustion produced a liquid H 2O product rather than a gaseous one. Values of the internal energies of the fuel and . those errors are due to the inaccuracy in the part of the experimenter and due to uncontrollable disturbances occurring during the conduct of the experiment. after the combustion. Upon the release of the gas from the bomb. At some point in every experiment.4 25. it has become necessary to weigh an initial amount of fuel greater than the amount indicated in the experiment. particularly before firing and at the near end of the combustion. Due to these losses. Such powdery white smoke was due to the uncombusted benzoic acid. So obtaining 3000L of water at 25°C was a crucial part of the experiment.9 24. certain losses in the amount of fuel occurs during pelletizing.Plot of temperature vs time for the combustion of Benzoic acid in trial 2. Initial temperature of water plays a significant role in this experiment. Calculation of the Cv of the calorimeter requires information on the internal energies of both the fuel and the platinum fuse.2 25. and the possible contribution of the stirrer to the heat evolving in the system. and in this case.8 0 200 400 600 time (s) 800 1000 1200 Figure 3 . Moisture was also found on the walls of the bomb.7 25.3 25.5 Temperature (°C) 25.Trial 2: 25. as observed after the experiment. since known values for the heat of combustion of certain substances like Benzoic acid are given at 25°C. can all cause discrepancies in the data that can be obtained from the experiment. As can be seen form Table 1. a powdery white smoke was observed to come out of the gas-filled bomb. For instance.
fuse can be obtained from various given data in literature. a large difference in the computed Cv of calorimeter is observed between trial 1 and trial 2.T3) = V3 (T3 . Such difference of Cv value for the two trials might also be due to the varying extents of combustion occurring in both trials.T3) V1 (19.25) °C + (3000-V1) mL (27– 25) °C = 0 V1 = 750 mL V1 + V2 = V3 V2 = 3000 mL – 750 mL = 2250 mL .T3) = V3 (T3 .T3) V1 (19.T3) + V2 (T2 . Corresponding calculation for the Cv of the calorimeter is shown below. The difference might be due to the differing amounts of sample used and the differing △T of combustion for each trial. And these possible causes can all be accounted as human errors.T3) + V2 (T2 . From these calculations.25)°C + (3000-V1) mL (28 – 25) °C = 0 V1 = 1000 mL V 1 + V2 = V3 V2 = 3000 mL – 1000 mL = 2000 mL SECOND TRIAL V1 T1 = 19°C V2 = 3000 mL – V1 T2 = 27° C T3 = 25°C V3 = 3000 mL Energy balance: H1 + H2 = H3 m1C 1T1 + m 2C2T2 = m 3C3T3 (constant Cp) ρ1V1T1 + ρ2V2T2 = ρ2 V2 T2 (constant ρ) V1 T1 + V2 T2 = V3 T3 Tref = T3 = 25°C V1 (T1 . COMPUTATIONS: Temperature and Volume Measurements of water: FIRST TRIAL At T1 = 19°C and T2 = 28°C V1 T1 = 19°C V2 = 3000 mL – V1 T2 = 28° C V3 = 3000 mL T3 = 25°C Energy balance: H1 + H2 = H3 m1C 1T1 + m 2C2T2 = m 3C3T3 (constant Cp) ρ1V1T1 + ρ2V2T2 = ρ2 V2 T2 (constant ρ) V1 T1 + V2 T2 = V3 T3 Tref = T3 = 25°C V1 (T1 .
228.29 ± 0. Therefore = –3.65 ± 0.24 J/g Solving for the △T compensation for the non-adiabacity of the bomb calorimeter: ( ) ( ) △ Trial 1: △ △ Trial 2 △ △ ( 0. Calculation for the CV of the calorimeter Benzoic acid undergoes an exothermic reaction: C6H5COOH (s) + 15/2 O2 (g) →7 CO2 (g) + 3 H2O (l) The isothermal conversion of one mole of benzoic acid to CO2 and H2O at 25°C (298.24 kJ of internal energy. would have a negative value. Converting this value into cal/g: ( )( )( )( ) Converting into J/g: ( )( =26.228.29 ± 0. Since this energy left the system.5167 °C ) ( ) ( ) ( ) )( ) ( ) ( ) Solving for the average △ △ for the 2 trials: ( ) .434. the molar internal energy change of combustion of benzoic acid. U(final) < U(initial).15K) liberates 3.24 kJ/mol.
Solving for the experimental value of the Cvcalorimeter: △ = = ( )( ) ( )( ) Platinum is found to be combustible. and its combustion reaction is given as: Pt(s) + O2(g) PtO2(s) △ ( ) ( ) But for a combustion process. ( Since ) ( ) ( ) ) ( ) therefore ( Solving for ( of platinum fuse )( ) ( )( )( )( ) For trial 1: = = *( )( ) ( ( ) )( ) ( )+ For trial 2: = = *( )( ) ( ( ) )(( ) ( )+ .
8 839. Winter.: 1 Evaluated by: ENGR.85 . Jessup. W. OLIVO BS ChE V Group No. de Paula. 2008. VIII. with 41 959.85 VII. Enthalpy of Combustion via Calorimetry. Bomb calorimeter – heat of combustion. 2010. Oxford.30 for trial 2.40 for trial 1 and 25 720. 1960. JOHN MARVIN C. It can also be concluded that the calorimeter was not 100% adiabatic since the corrected △T was not equal to the actual △T in both trials. Prepared by: ANNA MHAE I.) (Oxford University Press. National Bureau of Standards Monograph 7. MALONES Instructor . CONCLUSIONS Heat capacity of the calorimeter was proven to be determinable by combusting a reference substance with a known heat of combustion. 2002. REFERENCES R. UK). Physical Chemistry (7th ed.: 1 Section No. P.Solving for the average Cv = = 33 = 33 839. like benzoic acid. Robert Sonr. Experimental calculation of the Cv of the calorimeter yielded an average of 33 839.S. Precise Measurement of Heat of Combustion With a Bomb Calorimeter. Atkins and J.
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