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# EXPERIMENT #1

Bomb Calorimetry

I. Objective

## To be able to calibrate the bomb calorimeter by determining its heat capacity.

II. Theory
Calorimetric measurements involve the use of various temperature and energy units. In order to avoid
errors and confusion in the interpretation of these data, their relationships should be well understood.
Calorimetry is the science of measuring quantities of heat, as distinct from temperature. It is an important field
of analytical chemistry which deals accurately with measuring heats of reaction and finds application in fields
ranging from nutritional analysis to explosive yield tests (Melville, 2014). The instruments used for such
measurements are known as calorimeters. A calorimeter can be a simple container with good insulated walls to
prevent heat exchange with the environment. There are different types of calorimeter that are widely used
namely: (a) Oxygen bomb calorimeter; (b) Cup calorimeter; (c) flame calorimeter; (d) Solution calorimeter; and
(e) calorimeters used for kinetic studies. But among these types, the most common is the oxygen bomb
calorimeter. As shown in Figure 1 below, four essential parts are required in any bomb calorimeter: (1) a bomb
or vessel in which the combustible charges can be burned, (2) a bucket or container for holding the bomb in a
measured quantity of water, together with a stirring mechanism, (3) an insulating jacket to protect the bucket
from transient thermal stresses during the combustion process, and (4) a thermometer or other sensor for
measuring temperature changes within the bucket (Parr Instrument Company, 2009).

## Figure 1. Bomb Calorimeter (Polik, 2016)

According to the first law of thermodynamics, a change in internal energy depends on heat transfer between the
system and the surroundings (qsyst < 0 and qsurr > 0) and work done by/on the system (w):
U =qsyst +w
(1) (Eloranta, 2010)
Recalling that both q and w indicate changes in properties even though we have not written in front of them.
If we assume that only pressure (Pext) - volume (V) work is done and the volume is constant (i.e., V = 0), we

have:
w = (Pext)(V) = 0

## (2) (Eloranta, 2010))

Note that Pext denotes the external pressure against which the system does work. If the process is reversible,
the internal pressure (P) and Pext are identical. The first law at constant volume now becomes:
U = qsystem

## (3) (Eloranta, 2010)

In an adiabatic bomb calorimetric experiment, changes in the water bath temperature (T) are measured. If
the heat capacity Ccal of the calorimeter (surroundings) is known, thus the amount of the heat released by the
bomb (i.e., chemical combustion reaction) is given by:
qsystem = qsurr = Ccal x Tsurr

## (4) (Eloranta, 2010)

Hence, U is the quantity that an adiabatic bomb calorimeter determines directly through the measurement of
the heat absorbed by the surroundings (qsurr).
For the heat released in combustion Qcomb, it can be calculated from equation (5) wherein the heats of
combustion (Hc) for the benzoic acid (BA) sample and the fuse wire (FW) are added given by Leger and Teng
(1999):
Qcomb = Hc BA + Hc FW

## (5) (Leger and Teng, 1999)

Qcalorimeter and Quniverse refer to the heat gained by the calorimeter and the universe, respectively. Since
Quniverse is equal to zero, we have:
Qcombustion = -Qcalorimeter

## (6) (Leger and Teng, 1999)

The calorific value (heat of combustion) of a sample may be broadly defined as the number of heat units
liberated by a unit mass of a sample when burned with oxygen in an enclosure of constant volume. In this
reaction, the sample and the oxygen are initially at the same temperature and the products of combustion are
cooled to within a few degrees of the initial temperature; also the water vapor formed by the combustion is
condensed to the liquid state. A more exact definition would specify the temperature at which the reaction
begins and ends. However, the change in the heat of combustion with possible variations in the initial
temperature is so small that this specification is not necessary. Also, the initial and final temperatures are not
the same differing by the amount of temperature rise in the calorimeter but the effect of this difference is
small and usually it is neglected. Thus the term calorific value (or heat of combustion) as measured in a bomb
calorimeter denotes the heat liberated by the combustion of all carbon and hydrogen with oxygen to form carbon
dioxide and water, including the heat liberated by the oxidation of other elements such as sulfur which may be
present in the sample (Parr Instrument Company, 2009).

Many experiments conducted in bomb calorimetry include the calibration of the bomb calorimeter by
measuring its heat capacity. Once the heat capacity of the calorimeter is determined, heats of reaction of other
substances can now also be determined. Heats of combustion as determined in an oxygen bomb calorimeter,
are measured by a substitution procedure in which the heat obtained from the sample is compared with the heat
obtained from combustion of a similar amount of benzoic acid or other standardizing material whose calorific
value is known.
In principle, this involves comparing the corrected temperature rise of the calorimeter in an experiment
in which a known quantity of energy is supplied to it, with that produced in another experiment by combustion
in the bomb of a weighed sample of the given material. This method of using the corrected temperature rise of
the calorimeter to compare an unknown with a known quantity of energy eliminates some systematic errors.
These measurements are obtained by burning a representative sample in a high- pressure oxygen atmosphere
within a metal pressure vessel or bomb. Experiments conducted involving these measurements are often
called Calibration experiments. The energy released by this combustion is absorbed within the calorimeter and
the resulting temperature change within the absorbing medium is noted. The heat of combustion of the sample
is then calculated by multiplying the temperature rise in the calorimeter by a previously determined energy
equivalent or heat capacity determined from previous tests with a standardizing material. Corrections must be
applied to adjust these values for any heat transfer occurring in the calorimeter, as well as for any side reactions
which are unique to the bomb combustion process (Ginnings, 1970).
One of the corrections that needs to be addressed is the calorimeters nonadiabaticity. A bomb
calorimeter is only approximately adiabatic. In reality, there is a small heat leak through the dewar and the stirrer
does work on the calorimeter (wcalorimeter is not equal to zero). Noadiabaticity is corrected for with an
empirical radiative correction, RC. RC can be calculated by using the equation provided by:
(RC)

5(18 12 )+(6 0 )
6

(7)

## A. Preparation of the Benzoic acid sample

An approximately 1.5 g sample of benzoic acid was weighed using analytical balance and was firmly
pelletized using the sample pelletizer as shown in Figure 2 of the Appendix. One pelletized sample was prepared
for every trials. In the experiment, there were 2 trials conducted.

## B. Filling the calorimeter with water

Distilled water was placed in a plastic ice wrapper and was cooled in the refrigerator at the lab to prepare
the cold water needed for the experiment. The temperatures of the warm and cold water were then measured
using the thermometer and via energy balances, the required masses of cold and warm water were determined.
In calculating the required masses, the final temperature must be at 25 degrees celsius and that the calorimeter
water must be 3000 mL. After calculating the mass of the cold and warm water, they were measured using a
graduated cylinder and were immediately mixed together in a large container and was placed in the calorimeter.

## C. Attachment of the Platinum fuse

A 7 cm length of fuse was cut using a pair of scissors and was weighed using the analytical balance. In
the experiment, there were two pieces of 7 cm fuse that were prepared, one for each of the two trials. The bomb
head was then placed at the support stand and the fuse was attached between the two electrodes.
D. Securing of the sample in the bomb head
The pelletized Benzoic acid sample was carefully placed in the steel capsule and the fuse was bent using
a forceps to touch the top surface of the sample. The connection between the fuse and the top surface of the
sample was carefully checked because errors in the experiment could arise once this part of the procedure is not
correctly performed.

## E. Closing the Bomb calorimeter

The bomb head from the support stand was removed and was carefully placed in the bomb cylinder. The
screw cap was then secured and the oxygen and the gas release valves were then closed. The bomb calorimeter
used in the experiment is shown in Figure 3 of the Appendix.
F. Filling the Bomb calorimeter with oxygen
With the assistance from the laboratory technician, the hose from the oxygen tank was secured to the
bomb and the oxygen tank valve at the oxygen tank was opened.
The oxygen control valve was then slowly opened and the increase in the bomb pressure approximately not
exceeding to 590 psig was observed. After obtaining the desired pressure, the control valve was carefully closed.

## G. Pre-firing and firing the Bomb calorimeter

The two ignition wires were attached to the terminal sockets of the bomb head. The oxygen-filled bomb
calorimeter was then placed in the bucket of water and the screws at the calorimeter cover were secured to
close the calorimeter.
The bomb calorimeter was examined if it has any sign of weakness or deterioration to prevent errors in the
results of the experiment. The thermometer was lowered, the stirrer was turned on and temperature was
recorded for every 30-second interval for 6 minutes. For the firing proper, the firing button was pressed for about
1 to 2 seconds on the ignition unit. Temperatures were also recorded for every 30-second interval for additional
12 minutes. Hence, the total time for the recording of temperatures was 18 minutes.
H. Recovery of the combustion products
The stirrer was turned off and the calorimeter was opened to take the bomb out. The bomb was wiped
and cleaned by a towel in order to prepare it for the next trial. Next, the bomb was brought to an open area
outside the laboratory. The gas release valves were slowly opened before the screw cap to remove the residual
gas pressure. It was brought back inside the laboratory and necessary observations were made. The cap was
unscrewed and the bomb head was lifted to check for incomplete combustion inside. The mass of the capsule
and the fuse were measured after combustion using the analytical balance. Lastly, all parts of the calorimeter
were washed with distilled water and were dried using a clean towel.
Procedures from A-H were then repeated until a minimum of two trials were attained. Unfortunately in
the experiment, each group was just limited to having two trials each because of time constraints and availability
of the bomb calorimeter. All necessary data gathered from the experiment were systematically tabulated for the
interpretation of results.

## IV. Discussion of Results

The goal of the experiment is to calibrate the bomb calorimeter by measuring its heat capacity. Sample
Benzoic acid was used as a standardizing material whose heat of combustion is known. Temperatures at different
time intervals were recorded in a total duration of 18 minutes. Data taken from the different temperatures with
respect to time within the pre-firing and post-firing period are plotted in the Temperature rise curve as shown
in Figure 2 below. Parts of the graph are labelled correspondingly based on the different periods observed in the
experiment. The pre-period describes the initial period at time = 0 to the first 6 minutes. This portion represents
the data obtained before firing the bomb calorimeter. Based from the graph, trial 1 has higher temperature
values compared to trial 2. This was probably because the amounts of water used in each trial were not the same
thus, different temperature rise were achieved.
On the other hand, the portion of the graph labelled as rise period describes the post-firing data obtained
after firing the bomb calorimeter. It was observed that a gradual increase in temperature accompanied the firing
of the bomb. Based from the graph, an almost steep line was plotted which represents large temperature
changes in the sample as compared to the pre-period. Lastly, post-period portion of the graph describes the
temperatures obtained after the subsequent temperature rise. These were the data obtained until the rest of
the 18 minutes of the experiment. Temperature changes of the water were accounted in its heat capacity which
describes the amount of heat required to raise its temperature by 1 degrees Celsius. Hence, greater change in
temperature of water was observed in Trial 1 with the higher amount of water.

28.5

TTemperature (C)

28
27.5

27
26.5
26
25.5

25
24.5

Pre-period

Rise period

10

Post-period

15

20

Time (minutes)
Trial 1
Trial 2

## Figure 3. Temperature rise curve for Benzoic acid

To promote complete combustion of the sample, more than 97% excess air was introduced. Benzoic acid
reacts with the oxygen to produce combustion products such as soot and moisture. This is represented by the
combustion reaction:
C6H5CO2H + 7.5O2 = 7CO2 + 3H2O
This reaction was validated by observing the contents of the bomb head after the experiment. Along
the sides of the bomb head were minimal amounts of black substance which is probably the soot and ample
amounts of water. Data obtained after the experiment are summarized in Table 1 below. To account the
corrections in the calculated delta T, RC was calculated and subtracted to the obtained the delta T to have the
corrected delta T. Larger RC was obtained in trial 2 probably because of larger temperature intervals since less
heat was lost because most of the heat was absorbed by the greater amount of water.

## Table 1. Summary of the calculated data

Parameters
mass of combusted BA (g)
mass of unburned BA (g)
mass of combusted fuse (g)
RC (K)
T (K)
Cv (cal/K)
Cv, average (cal/K)
%excess air

Trial 1
0.9924
0.0002
0.00250
0.0267
0.8733
4309.01

Trial 2
0.9700
0.0040
0.0031
0.0342
1.0258
3772.56

3586.24 cal/K
97.044

250.72

Consequently, the change in temperature of the water in the second trial was lower compared to trial 1 as
exhibited by the value of its calculated heat capacity. The heat capacity of the calorimeter was determined using
the mass and internal energy of both the benzoic acid and the platinum fuse by using equation (8):

(8)
Results showed that the heat capacity (CV) of trial 1 was greater than trial 2. This obtained value illustrates
the effect of the amount of water used in the bomb calorimeter. For trial 1, a value of 3854.55 calorie per Kelvin
indicates that 3854.55 calories of heat energy is needed to raise the temperature of the bomb calorimeter by 1
Kelvin. Compared with trial 2 of 3317.94 cal/K, the lesser water used yielded the lower heat capacity. The
average heat capacity 3586.24 cal/K cal/K. The bomb calorimeter is now calibrated and can now be used to
determine the heat of combustion of other samples.

V. Conclusion
Bomb calorimeter calibration was accomplished by burning completely a sample of known heat of
combustion which is benzoic acid and in a pure state with known heat of combustion. Other factors that could
affect the determination of the heat capacity such as heat leaking out of the calorimeter, the work done by the
stirrer, and the heat generated by the fuse should be carefully considered. The heat evolved from burning the
benzoic acid and the platinum fuse wire was divided by the corrected temperature change in order to calculate
the heat capacity of the bomb calorimeter. Errors could arise if values in temperature changes, precision of
equipments used and temperature of water that were calculated.

VI. Recommendation
More accurate results could have been obtained if more advanced equipment were used and human
errors were reduced.

VII. References

## Eloranta, J. (2009). Experiment 1: Adiabatic Bomb Calorimeter, 0(5), 17.

Francis, W. M. (2016). Fuels and Fuel Technology: A Summarized Manual in Two Volumes. Elsevier.
Helmenstine, A. M. (2015, November 17). Combustion Reactions. Retrieved from About Education:
Jones, A. Z. (2015, October 31). Introduction to Heat Transfer - Does heat transfer? Retrieved from about

Parr Instrument Company. (2007). Introduction to Bomb Calorimetry. Parr Instrument Company, (483),
Perry, R. H. (2008). Perry's Chemical Engineering Handbook 8th Edition. The McGraw-Hill Companies, Inc.

. H. (2008). Perry's Chemical Engineering Handbook 8th Edition. The McGraw-Hill Companies, Inc.

VIII. Appendix
Raw data and Sample Calculations
Table 1. Raw Data for Masses and Volume
Parameters
Mass of Benzoic Acid (g)
Mass of Fuse (g)
Mass of the Capsule (g)
Mass of the Capsule and Pelletized BA (g)
Mass of the Capsule and Soot (g)
Mass of Unburned Fuse
Pressure (psia)
Volume of the Bomb (L)
*Mass of Burned Fuse(g)
**Mass of Combusted Benzoic Acid (g)

Trial 1
1.0092
0.0122
12.4420
13.4512
12.4588
0.0097
122.787
0.350
0.0025
0.9924

Trial 2
0.9772
0.0112
12.8032
13.7804
12.8104
0.0081
114.263
0.350
0.0031
0.9700

## Table 3. Raw Data for Temperatures with respect to time

Trial 1

Trial 2

Time (min)

Temperature (C)

0.0 (initial)
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0

26.000
26.100
26.140
26.160
26.170
26.180
26.200
26.200
26.220
26.220
26.225
26.240
26.260

6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0

26.500
26.800
27.400
27.600
27.700
27.780
27.820
27.900

Time (min)

Temperature (C)

0.0 (initial)
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0

25.140
25.360
25.400
25.440
25.440
25.480
25.480
25.500
25.500
25.520
25.540
25.540
25.550

6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0

25.780
26.280
26.700
26.980
27.140
27.260
27.320
27.400

Pre-firing

Post-firing

10.5
11.0
11.5
12.0
12.5
13.0
13.5
14.0
14.5
15.0
15.5
16.0
16.5
17.0
17.5
18.0

27.900
27.920
27.920
27.960
27.965
27.980
27.980
27.980
27.990
27.990
27.990
27.990
27.990
27.990
27.990
27.995

10.5
11.0
11.5
12.0
12.5
13.0
13.5
14.0
14.5
15.0
15.5
16.0
16.5
17.0
17.5
18.0

Sample Calculations:
Data from Trial 1
a. Mass of Combusted BA = (Mass of Capsule + BA) (Mass of Capsule + Soot)
= 13.4512g 12.4588g
= 0.9924
b. Mass of Combusted Fuse = Mass of Fuse - Mass of Unburned Fuse
= 0.0122g - 0.0097g
= 0.0025 g
Calculating the radiative correction using equation (7):
5(T18 T12 )+(T6 T0 )
6
5(27.99527.960)+(26.26026.0)
6

## c. Radiative Correction (RC) =

=
RC

= 0.0725 K

d. T = T12 T6 RC
T = 27.960 26.260 0.0725 = 1.6275 K

## U (benzoic acid) = -6318 cal/g

U (platinum fuse) = - 2.3 cal/cm (Parr Instrument Company, 2009)
= - 2.3 cal/cm (7 cm) = - 16.1 cal (1/0.0122g) = - 1319.6721 cal/g
T
= 1.6275 K
Mass of burned BA = 0.9924 g
Mass of burned Pt = 0.0025 g

27.420
27.460
27.480
27.500
27.500
27.515
27.520
27.520
27.520
27.520
27.525
27.525
27.530
27.530
27.540
27.540

CV =
=

## UBA mBA + UPt mPt

T

(6318cal/g)(0.9924g) + (1319.6721cal/g)(0.0025g)
1.6275 K

CV = 3854.55 cal/K

## Taking the average of the heat capacities of the two trials:

Cv,average =
=

Cv,1+Cv,2
2

3854.55 + 3317.94
2
= . /

## Percent excess air

Data from Trial 1
Volume of Bomb = 350 ml = 0.350 L
Pressure in Bomb = 108.097 psig + 14.7 psi
Pressure in Bomb = 122.797 psia
Gas constant, R = 0.08206 L-atm/mol-K (Perry and Green, 2008)
Temperature = 298.15 K

f.

## Oxygen supplied (mol) in the bomb at 298.15 K:

= PV/RT
1atm
(122.797 psia) (
(0.350L)
14.7psi)
L atm
(0.08206
) (298.15 K)
mol K
= .
Combustion reaction of Benzoic acid: C6H5CO2H + 7.5O2 = 7CO2 + 3H2O
Molecular weight of Benzoic acid = 122.12 g/mol (Perry and Green, 2008)
Theo O2 for BA = (mass of BA/122.12g-mol-1)(7.5)
0.9924

= (122.12) (7.5)

10

(Polik, 2000)

## Theo O2 for BA = 0.0609 mol

Combustion reaction of Platinum fuse: Pt (s) + O2 = PtO2 (g)
Molecular weight of Pt = 195.08 g/mol (Perry and Green, 2008)
Theo O2 for Platinum fuse = (mass Pt/ 195.08)(1)
= (0.0025 g/195.08) (1)
= 1.2815 x 10-5 mol
Total Theo O2 =0.0609 mol + 1.2815 x 10-5 mol = 0.0609 mol

## Calculating the percent excess air:

g. Percent Excess air
=

O2 supplied theo O2
x 100
theo O2
0.120 0.0609
x100
0.0609
= . %

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Photos/Pictures

## Name: Bryle Kristiann C. Camarote

Groupmates: Dion Paul Caspe
Smith Nuevaespana
Emmanuel Plaza
Date of Experiment: September 15, 2016
Date Submitted: September 26, 2016

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