South University of Science and Technology of China

Department of Materials Science and Engineering

Experimental Physical Chemistry
LAB 1 Heat of Combustion
1. Objective
1.1. To learn the definition of heat of combustion, and to know the difference and relationship

between the heats of combustion at constant volume and constant pressure.

1.2. To get familiar with the principle and assembly of a bomb calorimeter, and to learn the

experimental technique of calorimetry.

1.3. To measure the heats of combustion of sucrose and benzoic acid using a bomb calorimeter.

1.4. To calibrate the variation of temperature by Renolds correction curve.

2. Introduction
2.1. Combustion and calorimetry

In thermochemistry, the heat of combustion is defined as the heat released from the total

oxidation of 1 mole compound, where total oxidation refers to the formation of specified

combustion products such as CO2(g), H2O(l), and N2(g). Besides its importance in practice, the

heats of combustion are also of great use for calculation or estimation of the formation enthalpy

and bond energy of a given compound.

Calorimetry is one of the fundamental experimental methods in thermodynamics. By measuring

the rise in temperature, the heats of combustion at constant volume ( Qv ) and at constant pressure

( Qp ) can be determined under respective conditions. According to the first law of

thermodynamics, Qv equals to the change in internal energy , and Qp equals to the change in

enthalpy . If all gaseous reactants and products are considered as ideal gases, the following

relations are obtained

(2-4-1a)

(2-4-2b)
where is the change in the number of moles of moles of gas during the combustion; R is the

gas constant; T is the combustion reaction temperature.

There are different types of calorimeters. The bomb calorimeter used in this experiment is an

adiabatic calorimeter in which the temperature of the outer jacket keeps constant.

The main parts of the bomb calorimeter are illustrated in Fig. 2-4-1, and Fig. 2-4-2 gives a

cross-sectional diagram of the bomb calorimeter.

2.2. Oxygen bomb calorimeter

The basic principle of the oxygen bomb calorimeter is the law of energy conservation. The heat

of combustion at constant volume can be determined by burning a certain amount of the sample in

a bomb calorimeter and measuring the rise in temperature of the calorimeter system. Qv is

obtained from

(2-4-2)

where Wsample and M are the mass and the molar mass of the sample respectively; Qv is the heat of

combustion of the sample at constant volume; l and Ql are the length of the fuse and the heat of

combustion per unit of the fuse, respectively; W water and Cwater are the mass and the mass and heat

capacity of water when using water as the measuring medium; C calorimeter is the heat capacity of the

calorimeter, i. e. , the heat needed for a temperature increase by 1 ℃ in the bomb calorimeter

exclusive of the water; is the temperature rise of the water after the burning of the sample.
 To ensure the total combustion of the sample, high-pressure oxygen or other oxidants is filled

into the bomb calorimeter. Hence, the bomb calorimeter should be airtight and can withstand high

pressure and corrosion. The bomb is placed in a room temperature thermostatic water jacket. A

highly polished baffle-board is put between the outer water jacket and the bucket to reduce heat

loss due to radiation and air convection.

2.3. Renolds correction curve

Actually, the heat transfer between the bomb calorimeter and the corresponding surroundings

cannot be fully avoided. The variation in temperature caused by this effect can be calibrated by the

Renolds temperature correction curve. The detailed procedure is as follows.

Weigh an appropriate amount of sample whose combustion can bring a temperature rise of the

water by 1.5~2.0 ℃. Pre-adjust the temperature of the water to about 1.0 ℃ lower than the room

temperature. Do the experiment according to the procedures. Plot the recorded value of the water

temperature against time. A plot as shown in Fig. 2-4-3 can be obtained. Point H stands for the

starting of the burning reaction and the heat is transferred into the water; and point D is the

maximum temperature value observed during the burning process. Draw a horizontal line through

the room temperature point J to point I on the curve, and draw a vertical line ab through point I.

Then, points A and C can be obtained by extending FH and GD lines to line ab. The temperature

difference between point C and A is the calibrated . The AA' part in the correction curve is the

rise of temperature caused by the surrounding irradiation and the stirring during , the time

period from the ignition of the sample to the reach of room temperature for the system, which

should be eliminated. The CC' part is the temperature decrease due to the heat releasing from the

bomb calorimeter to the surroundings during , the time period from room temperature to the

temperature maximum at point D, which should however be considered for calculation. Therefore,

the temperature difference between point C and A reflects the actual temperature rise value due to

the combustion of the sample.

In some circumstances, the good heat insulation of the bomb calorimeter, the slight heat loss
and the large power of the stirrer ( which would introduce large amount of energy continuously )

will make the temperature maximum disappear in the correction curve, as shown in Fig. 2-4-4.

The calibration process is still the same as that described above.

In the present experiment, the temperature differences are measured by a precise thermometer

with digital output.

3. Apparatus and Reagent

Bomb calorimeter; Precise thermometer with digital output ( calibrated to 0.01℃ ); large oxygen

cylinder with regulator; Pellet press; Electric heater (500 W); Plastic bucket; Ruler; scissors;

Multimeter; Scale (10 kg); Thermometer (0~50℃); Clock; 1000 ml Beaker; Medical balance; Iron

fuse wire; Benzoic acid (AR); Sucrose (AR).

4. Procedure
4.1. Measurement of heat capacity of the bomb calorimeter

4.1.1. Preparation of samples

Roughly weigh out 0.95 g of benzoic acid using the medical balance, and make it into a round

pellet with the press. Get rid of the powder on the surface by gently knocking the pellet on a piece

of clean weighing-paper using a pair of tweezers, and then weigh the sample precisely to 0.1 mg

(4 decimal places) using an analytical balance.

4.1.2. Assembly the sample and fill the calorimeter with oxygen gas

Open the bomb, and clean and dry all inner parts of the bomb, especially the stainless steel wire

on the electrode. Check that the metal sample pan is in position, and then place the sample pellet
in its center. Cut a piece of iron fuse wire of about 18 cm in length, wind the center part of the fuse

wire in to a coil with about 5~6 circles utilizing an iron nail with a diameter of about 3 mm. Fix

the two ends of the wire coil onto the electrodes as illustrated in Fig. 2-4-2 and let the coil keep

good contact with the sample. Check that the fuse wire does not contact with the metal sample

pan. Measure the resistance between the two electrodes using a multimeter which should be

generally less than 20 Ω. Assemble the bomb, and replace the bolt at the gas inlet by the connector

of the oxygen-filling pipe. The other end of the oxygen-filling pipe is connected to the pressure

regulator on the oxygen cylinder. Open the main cylinder valve and fill the bomb to a pressure of

2 MPa controlling the flow of gas with the small control valve on the cylinder.

Close the main cylinder valve. Disconnect the sealed bomb. Release the residual oxygen in the

regulator. Screw on the bolt at the inlet. Check the resistance between the two electrodes with the

multimeter again. If the resistance is too high or there is a shortcut between the electrode and the

wall of the bomb, depressurize the oxygen and open the bomb to check over.

4.1.3. Temperature measurement

Weigh accurately 2.5 kg of water with the temperature adjusted to about 1℃ below the room

temperature in the water bucket. Immerse the bomb in the water bucket, assemble the stirrer, and

connect the two electrodes of the bomb to the ignition voltage supplier using a conducting wire.

After putting on the lid, determine the surrounding temperature (the J point in the Renolds

correction curve) by placing the probe of the precise thermometer with digital output into the outer

jacket, and then place the probe into the bomb system. Turn on the stirrer, and record the

temperature of the inner bucket every minute as precise as possible (with a precision up to

0.001℃) when it starts to increase steadily. After 10~12 min, press the ignition button on the

transformer for 4~5 s. Then, record the temperature every 15 s till the difference between two

consecutive readings is within 0.005℃, then continue to record the temperature every minute

again for a further 10~12min.

Switch off all electrical circuits, take out the probe of the digital precise thermometer and the

bomb, open the outlet of the bomb to depressurize the residual gas. Open the bomb and check the

completion of the combustion reaction. If all of the sample has been burnt, there should be no

obvious black carbon residue in the bomb. The experiment must be repeated, if carbon residue has
been observed. Calculate the actual length of the burnt iron fuse wire by measuring the length of

the residual fuse wire. Clean and dry all parts of the bomb finally.

The most important steps of this experiment are the successful ignition and the total combustion

of the sample.

4.2. Measurement of the heats of combustion of sucrose

Roughly weigh out 1.5 g of sucrose and then repeat the procedure described above.

5. Data Analysis
5.1. The heats of combustion for benzoic acid and the iron fuse wire are -26460 J·g -1 and -2.9

J·cm-1, respectively.

5.2. Plot the graph of Renolds correction curves for benzoic acid and sucrose, calculate the heat

capacity of the bomb calorimeter and heat of combustion at constant volume of sucrose ( Qv) from

T, and then calculate the heat of combustion at constant pressure of sucrose (Qp).

5.3. Present the measured data accurately based on the precision of the instruments associated with

this experiment, and point out the greatest inherent source of inaccuracy.

5.4. Literature data

Enthalpy of combustion at
Measuring conditions
constant pressure

, 20℃
Benzoic acid -771.24 -3226.9 -26460

Sucrose -1348.7 -5643 -16486

, 25℃

6. Questions and Further Thoughts

6.1. Why should the solid sample be pressed into pellets?

6.2. In calorimetry, what are the other cases in which Renolds correction curve should be

employed?

6.3. How to calculate the formation enthalpy of sucrose based on its heats of combustion data?