Experiment No. 1 CALIBRATION OF BOMB CALORIMETER I. OBJECTIVES a. To be familiar with the operation of a bomb calorimeter b.

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.

II.

It is more convenient to conduct the measurement oh heat of combustion of reactions at constant volume rather than at constant pressure. 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). If the compound being burned is known, 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. If the composition of the material is unknown, the difference between DU and DH is often unknown and therefore the results should be reported as DU. III. MATERIAL AND APPARATUS a. Materials and Reagent distilled water minimum of 3,500 mL distilled water for washing purposes benzoic acid minimum of 0.5 g Platinum fuse b. 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.

PROCEDURE a. PRECAUTIONS Certain precautions were observed while conducting the experiment. The laboratory technician made sure that the oxygen pressure did not exceed 590 psig (40 atm). The sample mass was also ensured to not exceed 1.5 g. 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, before firing. b. Preparation of sample( benzoic acid) Approximately 0.5 g of the sample (benzoic acid) placed in an ordinary paper was weighed using an analytical balance. The weighed sample was then pelletized in the sample pelletizer. The pelletizer was first cleaned to avoid any contamination on the sample. The sample was pelletized thoroughly before it was obtained from the pelletizer. Careful handling of the pelletized sample was done using the forceps. The pelletized sample was then weighed to account the losses during pelletizing. c. Filling of the calorimeter with water

The experiment required 3,000 mL of distilled water with a temperature of approximately 25 0.3 C to be filled in the bucket where the bomb is to be submerged, so that the standard heat of reaction can be obtained. The group has done certain preparations before obtaining the required water conditions. The temperature of water at room temperature was measured to be higher than 25C so the group decided to cool some water to lower the temperature to approximately 25C. Calculations employing heat balance was done in estimating the volume of water of different known temperatures to be measured. d. Attaching the Platinum fuse Eight centimeter (8 cm) platinum wire was cut with the use of a ruler and a scissor. The cut wire was then weighed in the analytical balance. The bomb head was placed on the support stand and the fuse was securely fastened between the two electrodes in the bomb head. e. Securing of sample in the bomb head The pelletized sample was carefully placed in the steel capsule using the forceps. The steel capsule was first made sure to be thoroughly cleaned, and it was weighed before the sample was placed in it. 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. f. 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 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. In closing the bomb properly, the screw cap was then set on the cylinder and was firmly turned down until it was very tight. g. Filling the bomb with Oxygen The control valve at the top of the bomb was opened. The hose from the Oxygen tank was connected to the control valve and was securely tightened. The Oxygen tank valve was then opened not more than one quarter turn. 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, in conformance to the safety precautions involve in conducting the experiment. The control valve was then closed. The whole procedure was done by an authorized laboratory technician who knew the whole process very well. h. Pre-firing The two ignition wires were attached to the terminal sockets on the bomb head. Then the Oxygen-filled bomb was slowly placed in the center of the bucket-filled with water. The set-up was then checked for any gas leakage by observing for continuous production of air bubbles. For leakages, it was required to remove the bomb from the water, release the pressure, and to fix

the leak, before starting the experiment again. Without the observation of leakage, it is needed to proceed by closing the cover and by seating the cover snugly against the calorimeter. The thermometer was then inserted in the cork and was inserted in the hole provided on the cover of the calorimeter, making sure that it reaches the water level in the bucket. The initial temperature of water was recorded. The stirrer was then turned on for 6 minutes, and the temperature of the water was read every 30 seconds. i. Firing of the bomb The ignition unit was plugged to the power source and was turned on. The firing button was then pressed for about 1-2 seconds. The temperature was recorded every 30 seconds for 12 minutes after firing. The time after firing at which the first temperature rise occurred was also recorded. Recovery of the combustion products After 18 minutes of observation period, the stirrer was turned off and all electrical connections were unplugged. Then, the calorimeter cover was opened and the bomb was lifted and was wiped dry. It was then brought outside the room, and the gas release valve was opened gradually to get rid of the residual gas pressure, before removing the screw cap. The gas that was released was then observed. The screw cap was removed and the bomb head was lifted and placed in the support stand. The interior of the bomb, particularly the capsule, was then examined for soot and other evidence of incomplete combustion. The capsule was again weighed to account for the materials that were formed in the capsule. The fuse was also measured afterwards. A second trial was then conducted using the same procedures.

j.

V.

ILLUSTRATION OF SET-UP

Figure 1 Parts and components of a bomb calorimeter.

VI.

DATA, ANALYSES AND RESULTS

Table 1 Measurements of reagents and materials before and after combustion. Initial Measurements: TRIAL 1 TRIAL 2 Mass Benzoic Acid (g) 0.5301 0.5128 Mass Capsule (g) 12.4553 12.6694 Mass of Pellet (g) 0.4968 0.4938 Mass Fuse (g) 0.0134 0.0129 Measurements after Combustion Mass of Capsule (g) 12.4625 12.6795 Mass of fuse (g) 0.0028 Mass of Soot Formed (g) 0.0072 0.0101 m benzoic acid 0.5029 0.5027 Table 2 Time and temperature measurements before and after firing. Time Temperature (C) st (seconds) 1 Trial 2nd Trial Stabilization period 0 24.8 24.9 30 24.9 24.9 60 24.9 24.9 90 24.9 24.9 120 24.9 24.9 150 24.9 24.9 180 24.9 24.9 210 24.9 24.9 240 24.9 24.9 270 24.9 24.9 300 24.9 24.9 330 24.9 24.9 360 = 6 min= T6 24.9 24.9 After Firing 390 24.9 25 420 24.9 25.05 450 25 25.1 480 25 25.2 510 25 25.2 540 25.2 25.3 570 25.3 25.35 600 25.4 25.35 630 25.4 25.4 660 25.4 25.4 690 25.4 25.4 720 = T12 25.4 25.5 750 25.5 25.5 780 25.5 25.55

810 840 870 900 930 960 990 1020 1050 1080= T18 Trial 1: T0 =24.8 C T6 = 24.9 C T12 = 25.4 C T18 = 25.6 C tfirst T rise = 40 s

25.5 25.6 25.6 25.6 25.6 25.6 25.6 25.6 25.6 25.6 Trial 2 T0 = 24.9 C T6 = 24.9 C T12 = 25.5 C T18 = 25.6 C tfirst T rise = 25 s

25.55 25.55 25.6 25.6 25.6 25.6 25.6 25.6 25.6 25.6

The experiment used benzoic acid, with a known heat of combustion, in determining the heat capacity of the calorimeter. The data presented in Tables 1 and 2 are the data necessary in order to calculate for the Cv of the calorimeter. These data were obtained from the experiment, before and after the combustion process. As can be seen on Table 2, the temperature rises very minimally, and the difference between the final and the initial temperature of water from zero to 18 minutes is a small value. Below is a plot of temperature vs time for the two trials. Trial 1
25.7 25.6 25.5 Temperature (C) 25.4 25.3 25.2 25.1 25 24.9 24.8 24.7 0 200 400 600 time (s) 800 1000 1200

Figure 2 - Plot of temperature vs time for the combustion of Benzoic acid in trial 1.

Trial 2:
25.7 25.6 25.5 Temperature (C) 25.4 25.3 25.2 25.1 25 24.9 24.8 0 200 400 600 time (s) 800 1000 1200

Figure 3 - Plot of temperature vs time for the combustion of Benzoic acid in trial 2. The plot represents the manner at which the temperature of the water increased after combustion. The temperature can be observed to be constant at some point in the graph, particularly before firing and at the near end of the combustion. The disappearance of the fuel in the capsule, as observed after the experiment, indicated that combustion had indeed occurred. Moisture was also found on the walls of the bomb, signifying that the combustion produced a liquid H 2O product rather than a gaseous one. Soot was found to be deposited in the capsule and such particular observation suggests that the combustion is incomplete. Upon the release of the gas from the bomb, after the combustion, a powdery white smoke was observed to come out of the gas-filled bomb. Such powdery white smoke was due to the uncombusted benzoic acid. Initial temperature of water plays a significant role in this experiment, since known values for the heat of combustion of certain substances like Benzoic acid are given at 25C. So obtaining 3000L of water at 25C was a crucial part of the experiment. As can be seen form Table 1, certain losses in the amount of fuel occurs during pelletizing. Due to these losses, it has become necessary to weigh an initial amount of fuel greater than the amount indicated in the experiment. The experiment is simple but it has become tedious due to the repetitions done every time mistakes are inevitably done. At some point in every experiment, errors arise, and in this case, 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. For instance, the inaccuracy in reading the temperature from the thermometer for every time interval can be cited as a human error. Some other unaccounted factors, like the probable contamination in the sample, the sample loss incorporated in attaching the fuse to the surface of the sample, and the possible contribution of the stirrer to the heat evolving in the system, can all cause discrepancies in the data that can be obtained from the experiment. Calculation of the Cv of the calorimeter requires information on the internal energies of both the fuel and the platinum fuse. Values of the internal energies of the fuel and

fuse can be obtained from various given data in literature. Corresponding calculation for the Cv of the calorimeter is shown below. From these calculations, a large difference in the computed Cv of calorimeter is observed between trial 1 and trial 2. The difference might be due to the differing amounts of sample used and the differing T of combustion for each trial. Such difference of Cv value for the two trials might also be due to the varying extents of combustion occurring in both trials. And these possible causes can all be accounted as human errors. COMPUTATIONS: Temperature and Volume Measurements of water:

FIRST TRIAL At T1 = 19C and T2 = 28C V1 T1 = 19C

V2 = 3000 mL V1 T2 = 28 C V3 = 3000 mL T3 = 25C

Energy balance: H1 + H2 = H3 m1C 1T1 + m 2C2T2 = m 3C3T3 (constant Cp) 1V1T1 + 2V2T2 = 2 V2 T2 (constant ) V1 T1 + V2 T2 = V3 T3 Tref = T3 = 25C V1 (T1 - T3) + V2 (T2 - T3) = V3 (T3 - T3) V1 (19- 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 = 19C

V2 = 3000 mL V1 T2 = 27 C

T3 = 25C V3 = 3000 mL Energy balance: H1 + H2 = H3 m1C 1T1 + m 2C2T2 = m 3C3T3 (constant Cp) 1V1T1 + 2V2T2 = 2 V2 T2 (constant ) V1 T1 + V2 T2 = V3 T3 Tref = T3 = 25C V1 (T1 - T3) + V2 (T2 - T3) = V3 (T3 - 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

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 25C (298.15K) liberates 3,228.29 0.24 kJ of internal energy. Since this energy left the system, U(final) < U(initial), the molar internal energy change of combustion of benzoic acid, would have a negative value. Therefore = 3,228.29 0.24 kJ/mol. Converting this value into cal/g:
( )( )( )( )

Converting into J/g: ( )( =26,434.65 0.24 J/g Solving for the T compensation for the non-adiabacity of the bomb calorimeter: ( ) ( ) Trial 1: Trial 2 ( 0.5167 C ) ( ) ( ) ( ) )( )

Solving for the average

for the 2 trials: ( )

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: = =
*( )( ) ( ( ) )(( ) ( )+

Solving for the average Cv =

= 33

= 33 839.8 839.85

VII.

CONCLUSIONS Heat capacity of the calorimeter was proven to be determinable by combusting a reference substance with a known heat of combustion, like benzoic acid. Experimental calculation of the Cv of the calorimeter yielded an average of 33 839.85 , with 41 959.40 for trial 1 and 25 720.30 for trial 2. 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.

VIII.

REFERENCES R.S. Jessup, 1960. Precise Measurement of Heat of Combustion With a Bomb Calorimeter. National Bureau of Standards Monograph 7. P. W. Atkins and J. de Paula, 2002. Physical Chemistry (7th ed.) (Oxford University Press, Oxford, UK). Robert Sonr, 2008. Bomb calorimeter heat of combustion. Winter, 2010. Enthalpy of Combustion via Calorimetry.

Prepared by:

ANNA MHAE I. OLIVO BS ChE V

Group No.: 1 Section No.: 1

Evaluated by:

ENGR. JOHN MARVIN C. MALONES Instructor

Comments:

Rating