1

Combustion Calorimetry

Please Note: Each lab group will be required to pick the compound they use in this experiment.
The compound must contain only carbon and hydrogen or carbon, hydrogen and oxygen. The
C
H or
f
H for this compound must have been determined in the last 20 years or longer than 70
years ago. Also the compound must be relatively inexpensive, be not acutely toxic and be
combustible (not overly volatile or deliquescent). Please provide a vendor as well as a price for
your sample. Your information is due one week before the lab begins.

Each person in each group must a separate primary reference for the
C
U for benzoic acid
without outside help.

I. lntroduction

In this experiment
C
H
O
will be determined and use to calculate
f
H
O
for your chosen
compound.
C
H will be obtained using an adiabatic, constant volume calorimeter (bomb
calorimeter) (Figure 1).



Figure 1- Schematic of adiabatic bomb calorimeter

The following reaction represents the typical combustion reaction in an oxygen bomb
calorimeter.

v
HC
hydrocarbon(solid or liquid) + v
O
2
O
2
(g) -----> v
CO
2
CO
2
(g) + v
H
2
O
H
2
O(l) + heat

where v
X
= the stoichiometeric coefficient for compound x

The heat released during combustion (q) is detected by the temperature increase recorded in
the calorimeter bucket. The system is composed of the sample, the oxygen gas, the bomb, the
bucket and water, stirrer and thermometer. This system is separated from the surroundings by an
2
adiabatic boundary. The adiabatic boundary is achieved by keeping the adiabatic jacket
temperature the same as the system temperature. For the calorimeter used in the experiment, this
equilibrium is accomplished by the addition of hot or cold water to the adiabatic jacket. A Parr
Model 1241 (Parr Instrument Co., Moline, IL) automatic adiabatic calorimeter will be used in
this experiment. The temperature adjustment keeping the jacket temperature the same as the
system temperature is done automatically.

Figure 2 is a more detailed picture of the oxygen bomb you will be using. The oxygen filling
valve is not shown but is directly behind the venting valve. Our bombs use two ignition leads and
solid samples are placed directly in the sample cup and not suspended above the cup as shown in
this drawing. Best results are obtained using ~ 1.0 g samples and 30.0 atm of oxygen gas.
Obviously the system must be sealed, consequently the bomb calorimeter reaction occurs under
constant volume rather than constant pressure conditions and the measured heat transfer is q
v

which is equal to
C
U.


Figure 2 - Parr oxygen bomb















3
II. Equations

The fundamental adiabatic, bomb calorimeter equation is given by equation 1a. Recall that in
a thermodynamic change at constant volume, no work is done.


Total System
C V
U C T = (1a)

Where:
Total System
V
C = total constant volume heat capacity of the system


Total System Water Calorimeter Analyte
V V V V
C C C C = + + (1b)


Total System
V
C will be a constant as long as the following conditions are met. Using the same
bucket and bomb for all work will keep
Calorimeter
V
C

constant.
Analyte
V
C will be hard to keep constant
but its contribution is so small that any error caused by varying sample size will be negligible.
Water
V
C accounts for about 75% of the total heat capacity of the system. This value is very sensitive
to the mass of water used. It is very important that the mass of water used in all work be kept
constant.

For benzoic acid samples:
C Total C Benzoic Acid C Fuse Wire
U U U = + (2)
For unknown solid samples:
C Total C X C Fuse Wire
U U U = + (3)
For unknown liquid samples:
C Total C X C Fuse Wire C Sample Pouch
U U U U = + + (4)

Total System
V
C is determined by burning samples of benzoic acid (the combustion calorimeter
standard with an accurately known value for
C
U) and then solving equation 1a for
Total System
V
C .

Once
Total System
V
C has been determined,
C
U
X
(kJ/mol) for the chosen compound can be
determined from equations 1 and 3 or 1 and 4.
C
H
X
(kJ/mol) can be calculated using equation 5.

( ) ( )
C X C X gas
H kJ mol U kJ mol n RT = + (5)

Care must be taken while doing the above calculations. The units on
C
U
Benzoic acid
,

C
U
fuse wire
and
C
U
sample pouch
will all be J/g.
Total System
V
C will have the units of J/C. The units
on
C
H
X
must be J/mol or kJ/mol.









4
III. Correction of
C
H
X
to standard state conditions

Remember standard state conditions for chemical reactions requires all reactants and products
to be at 298.15 K and all gases to have a partial pressure of 1.00 Bar (0.987 atm). The total
differential of enthalpy (equation 6) will give us the correcting equations we need. The first term
in equation 6 is the temperature correction term.


P T
H H
dH dT dP
T P

= +



(6)

Since our procedure reasonably approximates the standard state temperature conditions, no
temperature correction will be needed. However the partial pressures of oxygen gas and carbon
dioxide gas will be significantly different from standard state conditions, this correction will need
to be made. The second term in equation 6, which we will call H
pressure
, will help us make this
correction.
From lecture remember (H/P)
T
= - C
P
so;
o o
2 2 2 2 2 2
exp exp
p p
pressure O O P,O CO CO P,CO
p p
H C dP C dP =


where: = stoichiometric coefficient of oxygen or carbon dioxide, = Joule-Thompson coefficient,
and C
P
= molar heat capacity
Thermodynamic Data for CO
2
and O
2



Gas C
P
/(J mol K
-1
) /K

atm
-1


O
2
29.72 0.31

CO
2
37.14 1.10

Finally,
C
H
X
O
=
C
H
X
+ H
pressure
.

III. Procedure

1. Turn-on the water to the water heater and to the water cooler (same valve).

2. Turn-on the power to the water heater and water cooler.

3. After the water heater has come to temperature turn on the calorimeter power and
place the run/purge switch into the purge position.

4. The calorimeter should automatically adjust the adiabatic jacket to about 25C. This
temperature is not critical. Anywhere between 24 and 26C will be OK. If adjustment
is needed, the purge temperature can be changed using the jacket adjust dial. Be
careful, a small change in this setting makes a fairly large change in the resulting
purge temperature.



5
If the jacket temperature is below about 20 C, the automatic controller will not work
properly and hot water will have to be added manually using a toggle switch located
on the top control panel. This condition is usually indicated by a constant addition of
cold water to the jacket. To correct this problem hot water has to be added manually
until the controller seems to be OK. Correct functioning is usually indicated by a
cycling of hot and cold water being added to the jacket.

5. If this is the first run of the day, you will need to activate the calorimeter data
acquisition system by; (a) loading LabView / BOMBRUN) (b) mounting two
calibrated thermistors in the calorimeter, (c) connecting the thermistors to the
computer interface control box and (d) enter the A, B and C determined for the 20 to
30C calibration of each thermistor thermometer. When you run BOMBRUN, the
program will take you through the steps required to correctly incorporate the
thermistors into the data acquisition program. Once you have verified that you are
reading correct temperatures, save the correctly configured program to your flash drive
(using a name other than BOMBRUN) and go to step 6.

6. Disassemble the oxygen bomb and prepare the sample to be burned. For most
materials one gram of solid sample or one milliliter of liquid sample is usually
sufficient. One milliliter of water must also be added to the bomb before the
bomb is sealed. Contemplate why for the lab interview!

7. Specific instructions concerning fuse wire, sample size, sample preparation and
handling, bomb assembly and oxygen pressurization will be given in lab.

8. Remove the calorimeter bucket. Empty and dry the bucket if it contains water from a
previous run.

9. Place the assembled and pressurized bomb into dried bucket.

10. Using the thermostated filling burette, carefully add an accurately known mass of
about 2000 g of 25C water to the bucket. Remember all subsequent runs must use
this same mass of water.

11. Place the filled bucket with bomb assembly into the calorimeter.

12. Connect the ignition wires, close the calorimeter lid, and carefully lower the
calorimeter lid.

13. Move the run/purge switch to run and begin data acquisition.

This step is critical; no useful data will be collected if this step is omitted.

14. Start BombRun.

15. Using the balance control dial, adjust the adiabatic jacket temperature to match the
bucket temperature.

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16. Once the jacket and bucket temperatures are the same, take about 4 additional minutes
of data to establish a good starting temperature. Record this temperature in your lab
notebook. Ignite the sample.

17. Ignition of the sample is accomplished by depressing the ignition switch. Successful
ignition will be indicated by a rapid increase in the bucket temperature. (A noticeable
change of temperature occurs within 30 seconds after ignition.) The automatic
controller will keep the bucket and jacket temperatures nearly equal.

18. Continue collecting data for about 12 more minutes so that the temperature of the
system and the jacket have stopped increasing and are clearly constant. Record the
final temperature in your notebook. Stop BombRun. Once BombRun has stopped
taking data, the run is now completed, change the run/purge switch to purge. Purging
will drop the jacket temperature to about 25C in preparation for the next run.

19. While the jacket temperature is being reduced, you can remove the bomb and bucket
from the calorimeter. Remove the bomb from the bucket.

20. Pour the bucket water back into the holding tank of the filling burette.

21. Release the excess oxygen gas and exhaust from the bomb and then disassemble the
bomb.

22. Set aside the left over fuse wire for weighing. Weigh only unburned wire, fused globs
of the fuse wire are considered to have burned.

23. Check the inside of the bomb for complete combustion. If the inside of the bomb is
sooty, indicating incomplete combustion, the run probably will not be usable.

24. Thoroughly dry the bomb and bucket and prepare the bomb for the next run.

25. Calculate C
sys
or
C
U
X
and
C
H
X
for the run.

26. Ordinarily three calibration runs will be done with benzoic acid and three runs with
the chosen compound. It may take more than three runs with the chose compound
because not everything burns as easily or as completely as benzoic acid.

IV. Computer Programs

1. Using a specifically constructed Excel program, calculate
Total System
V
C . This program
must be ready before your first week with this experiment.

2. Using a specifically constructed Excel program, calculate
C
H
O
(kJ/mol) for the
chosen compound. This program must be ready before you begin the second week of
this experiment.



7
V. Test Data for Computer Programs

Program 1- Calculation of
Total System
V
C

mass benzoic acid 1.00315 g

C
U
fuse wire
-5858 J/g
mass of wire burned 0.00635 g
initial temp 24.396 C
final temp 27.018 C

Expected result:


Total System
V
C 10126.9J C = = 10126.9 J x deg
-1
(Your value may differ slightly,
about 10J C depending on the value of
C
U of benzoic acid you use.)

Use this value of
Total System
V
C for the following calculations.


Program 2 - Calculation of
C
U and
C
H
O
for C
6
H
6
O
2
(s).

Use this data if the unknown is a solid.

Total System
V
C 10126.9 J deg
-1

C
U
fuse wire
-5858 J/g
pressure of O
2
30.0 atm
mass of sample 1.1779 g
mass of wire burned 0.0073 g
initial temp 24.889 C
final temp 27.604 C
volume of bomb 336 mL

Expected results:

C
U = -2845.9 kJ/mol
C
H = -2847.1 kJ/mol
C
H
O
= 2846.2 kJ/mol













8
VI. Grading

Please note any data taken before you arrive will not be available for your use and will
need to be repeated by you at a later date.

You must clearly demonstrate that you are prepared to do the required lab work.

Lab Report (125 points)

Your report on this work must include at least the following information.

1. Give the balanced combustion reaction of the chosen compound.

2. Report value(s) of
C
U (benzoic acid) used in C
System
calculation. Give correct
reference(s).

3. Calculate C
sys
for your calorimeter system and report the average at 95% confidence
limits. (A number of points will be given based on your standard deviation.)

4. Calculate
C
H
O
(kJ/mol) for your chosen compound and report the average at 95%
confidence limits. (A number of points will be given based on your standard
deviation.)

5. Data tables as appendices. One table for standardization runs and one table for your
unknown compound runs. Tables must include proper column heading and
appropriate table titles.

6. From tabulated values of
f
H for CO
2
(g) and H
2
O(l), calculate
f
H
O
(kJ/mol) for your
chosen compound. You can use
f
H
O
values from your textbook. Show calculation.

7. Compare either
C
H
O
or
f
H
O
for your compound with primary literature values.
Give the correct literature reference for your source. Attach a copy of the article.

8. Calculate the most probable errors in C
total system
and
C
H. Clearly indicate the
estimated errors you used in these calculations.

9. Discussion of why any run was discarded.

10. Intelligent discussion comparing experimental results to literature value, including the
significance of errors.








9
VII. Interview Questions

1. Derive the adiabatic combustion calorimeter equation:
Total system
C Total V
U C T = .

2. How is
Total system
V
C determined?

3. What is the combustion equation for benzoic acid?

4. What is
C
U for benzoic acid?

5. Structure of the unknown compound. Any special handling or safety concerns?

6. What is the combustion equation for the unknown compound?

7. What is the value of n in equation 5 for the unknown compound?

8. Using a bomb volume of 336 mL and assuming CO
2
(g) is ideal, calculate the partial
pressure of CO
2
in the bomb after the complete combustion of 1.00 g of your unknown
substance. You can assume the final temperature of the reaction is 28.00 C.

9. Review the basic procedure for this experiment for the combustion of benzoic acid.

10. Why is 1 mL of H
2
O added to reaction chamber?

11. What are the major sources of error in the determination of
Total system
V
C ?

12. Others???


VIII. References

1. Sime, R. J. Physical Chemistry: Methods, Techniques and Experiments; Saunders: San
Francisco, 1990; p420.

Please note: Sime's discussion is fine but her main working equation (eq 3-6) is not entirely
correct. Also, since we can flush our systems, we do not have to correct for the formation of
nitrogen oxides.

2. Shoemaker, D. P., Garland, C. W., Nibler, J. W. Experiments in Physical Chemistry;
M
C
Graw- Hill: New York, 1996; p152.




Author: Roger Hoburg Editing: Ed Tisko