Experiment 1: Adiabatic Bomb Calorimeter

(Dated: September 27, 2010)

I.

INTRODUCTION

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. The heat of combustion can be most conveniently measured using an adiabatic bomb calorimeter. In
such calorimeter, the combustion reaction occurs in a closed container under constant volume (bomb). The bomb
is immersed in a weighted quantity of water and surrounded by an adiabatic shield that serves as a heat insulator.
Continuous stirring ensures that heat is distributed evenly in the calorimeter. The bomb and the water bath, which
are in direct thermal contact, constitute an adiabatic bomb calorimeter. In this experiment the heat of combustion
of an organic compound is determined using a commercial Parr adiabatic bomb calorimeter. The heat of combustion
is directly related to important quantities such as the internal energy and enthalpy of a chemical reaction. A more
detailed overview of the thermodynamic approach can be found from Refs. [13].
II.
A.

THEORY

Internal energy of combustion

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)

Recall 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)

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 = qsyst

(3)

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, the amount of the heat released by the bomb (i.e., chemical
combustion reaction) is given by:
qsyst = qsurr = Ccal Tsurr

(4)

Thus U is the quantity that an adiabatic bomb calorimeter determines directly through the measurement of qsurr .
B.

Enthalpy of combustion

The enhalpy (H), which in the present case is enthalpy of combustion, is defined as:
H = U + PV

(5)

and correspondingly a change in H (denoted by H) is given by:

H = U + (P V ) = U + |P {z
V} +V P = U + |V {z
P} 6= U
=0

Typeset by REVTEX

6=0

(6)

From the above expression, we see that U and H would be identical only if the pressure in the bomb remains
constant. If the amount of gases in the bomb remain constant, P would be zero and thus U = H. However,
in most combustion reactions the molar amounts of gases change and therefore a method for calculating the (P V )
term in Eq. 6 is required. If we assume that the gaseous components in the bomb behave according to the ideal gas
law (P V = ngas RT ), we can write:
(P V ) = R(ngas T ) = RT ngas + Rngas T RT ngas
| {z }

(7)

small

where R is the gas constant (8.31 J mol K ). The term denoted by small can be neglected when changes in
temperature are small (couple of C). Note that ngas can be either positive (the amount of gaseous components
increase) or negative (the amount of gaseous components decrease). Also the contribution of liquids and solids to the
P V ) term is negligible.
Example. The combustion reaction of benzoic acid at 25 C is:
C6 H5 COOH(s) + 7.5O2 (g) 7CO2 (g) + 3H2 O(l)

(8)

In this case, for one mole of C6 H5 COOH(s), ngas = 7 7.5 = 0.5 mol. Hence for the combustion of one mole of
benzoic acid we have:

1
J
(298 K) = U 1240 J
H = U + mol 8.31
2
mol K
III.

(9)

APPARATUS AND CHEMICALS

A commercial bomb calorimeter (Parr) is a self-contained instrument used in determination of heats of combustion
of certain fuels and pure organic substances. The results obtained are sufficiently precise to make them of extreme
importance in most commercial and laboratory procedures concerned with heats of combustion.
The combustion bomb, made of corrosion-resistant metal, holds the sample whose heat of combustion is to be
measured. The sample is held in a cup as shown in Fig. 1. Fig. 2 shows how the ignition wire, used to start the
combustion reaction, is attached to the electrodes. After the sample and the wire have been properly placed in the
bomb, it is charged with oxygen gas from a commercial cylinder to the pressure of about 25 atm.

FIG. 1: Schematic of the sample support stand. Note positioning of the ignition wire (about 1 mm from the sample but not
touching it).

The assembled bomb is then placed in a bucket containing a specified quantity of water. The temperature rise
accompanying the combustion is read from a thermometer. A stirrer effects an even distribution of the water. The
bucket in turn is surrounded by an insulating air space, which prevents, as far as possible, heat leakage to the
surroundings.
2

FIG. 2: Attachment of the nichrome ignition wire. The caps on the electrodes fix the ignition wire.

First, it is necessary to obtain the heat capacity of the calorimeter system (Ccal ). This is the number of calories
necessary to raise the temperature of the entire calorimeter system by one degree centigrade. This is found by burning
a sample material of known heat of combustion. Benzoic acid of high purity is usually employed. The temperature
rise due to the sample is noted, and the number of joules of heat released in the combustion is calculated. These two
values enable one to calculate the heat capacity of the calorimeter system. This is then used to calculate the heat of
combustion of the assigned material.
Required materials: (I) Parr calorimeter system including firing mechanism, stirrer, etc., (II) pellet press, (III) two
digital thermometers with 0.01 C accuracy, (IV) ignition wire, (V) oxygen cylinder, (VI) benzoic acid, and (V)
unknown sample (naphthalene).
IV.

SAMPLE PREPARATION AND MEASUREMENT

Task overview: Carry out at least three independent measurements of the benzoic acid standard and at least three
independent measurements of the unknown sample (i.e., naphthalene).
Pellet preparation: Care must be taken to avoid overcharging the bomb for it must be realized that the peak pressure
developed during combustion is proportional to the size of the sample and to the initial oxygen pressure. Pellet size
should be limited to not more than 1.1 g. Prepare the pellet:
1. Weigh out approximately 1.0 g of sample. Grind it in a clean mortar and pestel.
2. Use the pellet press to make a pellet and weigh it.
3. Carefully place it in the sample cup with tweezers. Do not touch it with your hands!
Connect the ignition wire:
1. Measure out approximately 10 11 cm of wire and weigh it. It will also be necessary to weigh any unburned
wire after combustion since this is an important factor in the calculations.
2. Set the bomb head in the support stand and attach the length of nichrome fuse wire as illustrated in Fig. 2. A
pair of tweezers may be helpful in attaching the wire to the electrodes. Insert the wire through each eyelet then
slide each cap downward to complete the connection.
3. Place the sample cup (with the sample sitting in the center of the cup) in the cup holder and bend the nichrome
wire in a V-shape. Position the wire so that it almost touches the surface of the pellet (about 1 mm separation).
Fig. 1 illustrates the proper installation and sample placement. Make sure that the wire does not touch the
cup.
Liquids in the bomb: Pipet 1.0 mL of deionized water into the bomb to absorb the oxides of nitrogen formed from
nitrogen present in the oxygen mixture.

Close the bomb assembly:

1. Care must be taken not to disturb the sample when sealing and charging the bomb. Slide the head assembly
into the bomb cylinder, screw open the vent cap on the head assembly to allow air to be expelled, and push the
head down as far into the cylinder as it will go.
2. Close the vent cap tightly. A tight seal is required to prevent oxygen leaks.
3. Check the circuit with an ohmmeter. If the resistance is too large (>> 100 ), open the bomb and check the
wiring.
Install the oxygen connection:
1. Carefully secure the bomb in the bench clamp.
2. Slip on the oxygen tank connection hose to the pin on the head assembly.
Fill the bomb:
1. Open the oxygen tank valve. Open the regulator valve slowly and watch the gauge as the bomb pressure rises
to the desired filling pressure (25 30 atm). Once this pressure is reached close the control valve and then the
tank valve. Note: If the bomb is filled too quickly you can blow your sample out of the sample cup. Warning:
Do not exceed the specified pressure!
2. Use the quick-release valve to quickly remove the oxygen tank connection to minimize oxygen escape. Slight
leakage is normal but continuous leakage is a problem.
Possible problems:
1. If there is a continuous escape of gas from the bomb head connections once the oxygen tank valve is unscrewed
the bomb is defective and should not be used.
2. If the bomb will not hold pressure and you can hear oxygen escaping around the vent cap, then the cap is not
sealed tightly enough. Tighten down the screw cap by hand again and try to pressurize the bomb. If you are
not successful after one or two attempts use a new bomb do not fire a leaking bomb!
3. If too much oxygen should accidentally be introduced into the bomb, do not proceed. Unscrew the oxygen tank
connection and exhaust the bomb in the hood. This can be done by opening the vent cap. Reweigh the sample
before repeating the filling procedure.
Operating the calorimeter:
1. Remove the lid and place it on the ring stand. Check to see that the bucket is resting properly in the jacket,
noting the four pegs on the bottom of the jacket, which hold the bucket in place.
2. Carefully place the charged bomb in the bucket, noting that it rests on the raised circular area on the bottom
of the bucket.
3. Connect the ignition wire to the terminal socket on the bomb head. Fill the bucket with the 2 L of water. Make
sure that the digital thermometer can measure the initial water temperature. A typical temperature increase
during the experiment will be around < 4 C.
4. Set the cover on the jacket. The screw attached to the lid fits into the screw hole in the ledge of the jacket.
5. Turn the stirrer by hand to be sure that it runs freely, then slip the drive belt onto the pulley. If the belt does
not work properly, rubber bands can be used.
6. Insert the thermometer sensor probe into the calorimeter top so that the end of the sensor touches the water.
7. Connect the two lead wires on the ignition unit to the calorimeter. Do not press the firing button unless the
lead wire inside the jacket is connected to a bomb.
4

8. Plug in the calorimeter, ignition unit (use the 10 cm connector and ground) and timer. If the stirrer does not
turn automatically check to see that it is turned on.
9. Let the stirrer run for 5 min to reach equilibrium. At the end of this period start the timer, and read and record
the temperature at one-minute intervals for 5 min. At the start of the sixth minute stand back and fire the
bomb by pressing the ignition button and holding it down for about 5 s (until the light goes out). Caution:
Dont have any parts of the body over the calorimeter when firing the bomb. Continue to stand
clear for 30 s.
10. The temperature should start to rise within 20 s of firing. Take the first temperature reading at 30 s and
continue to take temperature readings every 15 s for a period of 2 min. The temperature should be read to the
nearest 0.02 C. The reading lens is not required at this point.
11. After this two-minute period record the temperature to the nearest tenth (ca. 0.002 C accuracy) with the aid
of the reading lens at one-minute intervals until the difference between successive readings is zero (or perhaps
becomes negative). This will take approximately five minutes. Accurate time and temperature observations
must be recorded to identify certain points needed to calculate the calorific value of the sample. Usually the
temperature will reach a maximum and then drops very slowly. Possible problems:
(a) No significant temperature rise (1 C within 1 min). Check to see that the ignition unit is plugged in and
all electrical connections are tight. Ignite the bomb again.
(b) If this does not solve the problem it will be necessary to turn off all electrical connections, discharge the
bomb in the hood and open it up. Place the bomb in the hood and open the valve to release the pressure.
If the pellet is still intact but fuse wire is partially burned re-wire the bomb, weigh the pellet again, charge
the bomb and ignite it again. If the pellet is only partially burned start over.
12. After the last temperature reading, turn off all the electrical connections, remove the drive belt, and place the
cover in support ring. Remove the ignition wire from the bomb, lift the bomb out of the bucket and wipe off
any excess water. Open the valve cap and discharge the bomb in the hood. Unscrew the cap, lift the head out
of the cylinder, and place it on the support stand.
13. Weigh any unburned fuse wire still attached to the electrodes and possible pieces of molten wire. When analyzing
your results, you will need to subtract this weight from the total fuse wire burned. Examine the interior of the
bomb for soot or other evidence of incomplete combustion. If such evidence is found the test will have to be
discarded.
V.

UTILIZATION OF DATA

Plotting the data:

Plot the (temperature, time) data for each run as illustrated in Fig. 3. Note the important points in the graph
denoted by i, a, b, c, and f. The point a denotes the time of firing of the bomb, b the position where the
temperature reaches 60 % of the total change, and c the time of maximum temperature (i.e., end of the reaction).
Points i and f denote the initial and final points of measurement, respectively. The accuracy for reading the points
should be to nearest 0.1 min. A simple approach for obtaining the temperature rise would consist of subtracting the
initial and final temperatures (i.e., T = Tc Ta ). However, if the temperature is not stable in the initial (i < t < a)
and final (f > t > c) periods, baseline correction must be applied. If the baseline is assumed to be linear, the rates
of change can be obtained by using a difference approximation:

r1

Ta Ti
Tf Tc
and r2 =
ai
f c

(10)

The baseline is evaluated for both initial and final temperatures about point b:
T = (Tc r2 (c b)) (Ta r1 (b a)) = Tc Ta r1 (a b) r2 (c b)
This is the expression for the baseline corrected temperature rise.

(11)

FIG. 3: An example of (temperature, time) data plot showing the positions for reading Ti , Ta , Tb , Tc , and Tf . For definitions
of points i, a, b, c, and f see the text.

Heat capacity of the calorimeter

Before Eq. (4) can be applied to find qsys (and U ), Ccal must be determined. In this experiment a specified amount
of benzoic acid will be used as a standard. By measuring the T (see Eq. (10)) using this standard, the heat capacity
of the calorimeter can be calculated as follows:
Ccal =

nqstd,surr + mwire qwire,surr

T

(12)

where n is the amount of benzoic acid in the pellet (mol), qstd,surr is the known heat of combustion of benzoic
acid that is released to the surroundings (the literature value [1] is: qstd,surr = qstd,sys = (H RT ngas )
= (3226.9 1.2) kJ mol1 = 3225.7 kJ mol1 at 25 C; the molar enthalpy the (P V ) correction),
mwire (g) is the amount of the fuse wire used in the experiment, and qwire,surr is the heat of combustion per one
gram of fuse wire (5.858 kJ g1 ; type Parr 45C10 nickel chromium fuse wire). Note that here Ccal is a positive quantity.
Heat of combustion of the sample
After determining Ccal , one can use this value (average of the runs) to calculate the gross heat of combustion (J
mol1 ) of the sample in question:

U = q sys =

q surr
| {z }

sample + wire

Ccal T mwire qwire,surr

q wire,surr =
n

(13)

where the over bars highlight that we are dealing with molar quantities and n denotes the molar amount of the
substance. Note that Eq. (12) is essentially identical to Eq. (4) with the exception that it is written in terms of molar
quantities and it includes the fuse wire correction. The fuse wire used for igniting the sample is partly consumed in
the combustion. Thus the fuse generates heat both by the resistance it offers to the electrical current and by the heat
of combustion of that portion of the wire, which is burned. The heat generated by the resistance is constant and
small and thus can be neglected. However, the amount of wire consumed will vary from test to test and therefore a
correction must be made to account for the heat of combustion of the metal.
Enthalpy of combustion
According to Eqs. (5) and (6), the enthalpy of combustion is related to the heat of combustion by the follow relation:
H U + RT ngas
6

(14)

where the overbar again indicate molar quantities. Recall that both H and U here are negative because the system
is releasing heat during combustion. The combustion reaction for naphthalene is:
C10 H8 (s) + 12O2 (g) 10CO2 (g) + 4H2 O(l)

(15)

From this equation, we can see that ngas = 2 for one mole of substance.
VI.

ERROR ANALYSIS

In this case, a simple error analysis is sufficient. Estimate the error in Ccal , U and H by calculating the standard
deviation of these variables. The following relations should be used:

Average of x = x =

N
1 X
xi
N i=1

(16)

vP
u
2
u
N (xi {x})
t i=1
Std. deviation of the mean of x =
N (N 1)
where xi are the data points (here Ccal , U or H) and N is the number of points. Note that here the number of
points is quite small and thus the error estimate may not be very accurate. See the general laboratory manual for
more information.
VII.

WRITTEN LABORATORY REPORT

Follow the general instructions for written laboratory reports. In addition, include the requested data in the
following section:
Results. Include the mean value from the repeated experiments as well as the simple error analysis (see Sec. VI) for
both the standard benzoic acid reference and the real sample. Find the literature value for your sample and compare
it to the value you obtained. If the results are different then discuss why this is so.
VIII.

REFERENCES

[1] P. W. Atkins and J. de Paula, Physical Chemistry (7th ed.) (Oxford University Press, Oxford, UK, 2002).
[2] R. J. Silbey, R. A. Alberty, and M. G. Bawendi, Physical Chemistry (4th ed.) (Wiley, New York, 2004).
[3] R. Chang, Physical chemistry for the chemical and biological sciences (University Science Books, Sausalito, California,
2000).