Jenny Jiou

03/09/16

The Heats of Combustion and Formation of Naphthalene

By Jenny Jiou
Partner: Daniel Gonzalez
Class: CHEM 4473.001

Jenny Jiou
03/09/16

Introduction
To find heats of combustion for certain reactions, it is feasible to use a bomb calorimeter.
Due to heavy insulation, a calorimeter is close to a perfect adiabatic. The system is isolated from
the environment by two liters of water surrounded by air insulation. This way, combusting a
chemical sample in the calorimeter and using temperature measurements makes it possible to find
the heat released. A substance with a known heat of combustion such as benzoic acid is used to
determine the heat capacity of the calorimeter. Once that value is known, the heats of combustion
for other chemical samples are found by combusting them, too.
The determined heats of combustion may be used to find experimental values of the
standard heats of formation of the different chemicals combusted. The chemical equations for the
combustion of the organic sample and the standard heats of formation of the combustion products
(carbon dioxide gas and liquid water) may be combined and manipulated using Hesss law so that
the sum of the reactions is the formation equation for the chemical sample. The heats of reaction
are summed accordingly (literature values are used for the formation of the combustion products)
and yield the value for the standard molar heat of formation for the sample.
Equation (1) helps calculate the temperature rise in the calorimeter, and it assumes the
pressure is constant and that r1 and r2 are relatively small but cannot be ignored1:
T-(Tf-Ti)- ( ) (td-ti)-( )f (tf-td)

(1)

where T is the temperature rise, ti is the time of firing the bomb, td is defined as the first point
after firing the bomb for ease in calculation, tf is the time at the beginning of the curve off, Ti is
the temperature at ti, Tf is the temperature at tf, ( ) is the rate of temperature rise in the preperiod,

and ( )f is the rate of temperature rise in the curve off to the maxiumum temperature. However,

Jenny Jiou
03/09/16
Now, Ucomb refers to the heat released for the combustion of napthalene and is given by
Ucomb = -CcalT UFE

(8)

The moles combusted, ncomb, is found by

ncomb = (weight of sample)/(molecular weight of chemical)

(9)

This equation assumes the entire mass of the sample was combusted and that the sample
was pure. The assumptions probably introduced a significant amount of error. The change in
moles of gas in the calorimeter for each mol of sample undergoing combustion is given as
ngas = ngaseous products ngaseous reactants

(10)

The assumption in this equation is that the water formed in combustion is a liquid instead
of a gas. This assumption is valid because about one ml of distilled water was added at the bottom
of the calorimeter, enabling the creation of a liquid-gas equilibrium of water and a saturation of
water vapor at that pressure. When the combustion reaction took place, the water that formed
would necessarily be in the liquid state since the final temperature is at room temperature, and
water is liquid at that temperature. Also, introducing pure oxygen to the bomb would increase the
pressure in an isochoric chamber, thus ensuring that the water would be liquid.
For a process with constant volume such as combustion in an isochoric calorimeter, the
equation for the change in internal energy U is
U = Q W = Q pV

(11)

where Q is the heat absorbed, W is the work done on the system, p is the pressure, and V is the
volume. Since the volume is constant, equation (11) becomes
U = Q

(12)

Jenny Jiou
03/09/16

Methods
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 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 Figure 2 and it also shows how the ignition wire, used to start
the combustion reaction, which 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. The assembled bomb is then
placed in a bucket containing 2.00 L of water. The temperature rise accompanying the
combustion is read from a thermometer. A stirrer effects an even distribution of the water. The

Jenny Jiou
03/09/16
3. Set the bomb head in the support and 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)
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.
2. Close the vent cap tightly. A tight seal is required to prevent oxygen leaks.
Install the oxygen connection:
1. Slip on the oxygen tank connection hose to the pin on the head assembly.
2. Open the oxygen tank valve and then open the regulator valve slowly to purge the
bomb for a couple of minutes
3. Close off the regulator and tighten the vent cap on the bomb to prevent O2 from
escaping. Turn on the regulator and watch the gauge as the bomb pressure rises to the
desired filling pressure (25 30 atm).
4. Once this pressure is reached close the control valve and then the tank valve.
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. Do not fire a leaking bomb!

Jenny Jiou
03/09/16
10. Take the temperature reading at 30 s intervals for 20 minutes. Usually the temperature
will reach a maximum and then drops very slowly.
11. 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.
12. 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.
Possible problems:
1. 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.
2. 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.

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Jenny Jiou
03/09/16
The following sample calculations for T and the heat capacity of the bomb.

Using these equations, a table of the T, U tot, and C(s) was calculated.

With the heat capacity of the bomb solved, the determination the heat of combustion and
formation for naphthalene was determined by two runs in the bomb calorimeter.

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Jenny Jiou
03/09/16
The terms were all solved for individually before the standard deviation was taken.

Discussion
The naphthalene results for the heat of combustion were drastically different from the
literature value for heat of combustion, -5150.09 kJ/mol, and heat of formation, -71.67 kJ/mol,
suggesting that there was significant error in not having complete combustion or the measurements
not accurate in one of the runs. When attaching the wire to the sample, mass could have been lost
during that time. The contact on the wire and accidental drop factors into the mass loss that was
not accurately recorded. This mass loss can explain the problems seen with trial 1 of naphthalene.
If the mass of the pellet was around 0.8054 g then the combustion of the sample will be closer to
trial two giving off results closer to the literature value for both heats of combustion and formation.
The other location where mass could be loss is the addition of oxygen. If the oxygen was purged
or added too rapidly, the sample could potentially bumb caussing residual loss inside the bomb
leaving this error unaccountable. Since the bomb is not perfectly adiabatic the temperature change
corrections is close but not exact to the bombs rate in loss of energy to the surrounding. Therefore
a small evaluation errors can arise. When evauating under a ideal gas and approximating the
temperature to 298 K, trial two agreed with the literature value by having an error of 2.61 % in
heat of combustion and 12.4% in heat of formation. The dependence of temperature on the heats
is undenieable since the internal energgy is dependent on temperatur change. Although, it is the
energy of the system that creats the thermal energy.

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