Heat of Combustion: Bomb Calorimetry

2/4/2015
Hannah Pennington

Introduction

Conversion between various units of energy are

1 Cal = 1000 cal = 4.184 kJ.
The following table lists properties of two of the substances participating in
the combustion reaction.
Liquid Water:
g
Molar Mass
18.0153 mol
Density at 25 C 0.99704 cmg 3
Heat Capacity
75.38 molJ K

Benzoic Acid:
Molar Formula
C7 H6 O2
g
Molar Mass
122.1213 mol
kJ
Enthalpy of Combustion -3228. mol

The combustion reaction for benzoic acid is as follows:

C7 H6 O2(s) +

15
2

O2(g) 7 CO2(g) + 3 H2 O(l) .

We can calculate the energy of combustion,

Urxn

= Hrxn - nRT
kJ
= -3228. mol
- (7- 15
) 8.314 molJ K (25.0 C+273.15) K
2
kJ
= -3227. mol .

Calorimetry measures the changes in heat. Experimentally, there are

multiple processes that allow for this measurement.
Constant-Volume Calorimetry: A constant-volume adiabatic bomb
calorimeter is container which aims to thermally isolate the system inside through a tight seal and thick stainless steel barrier. The reaction
occurs in oxygen at 30 atm, while an electrical discharge serves to start
the reaction. Surrounding the system containing the reaction with water, we can use the thermodynamic properties of water to interpret
the thermal changes in the reaction chamber. This mechanism for
calorimetry is often used to determine the caloric content of food and
other energy sources.
Constant-Pressure Calorimetry: When taking place under atmospheric conditions, the change in heat of the system can be accepted
as equal to the change in enthalpy. Eliminating heat exchange with
1

the surroundings through doublelayered insulation, we can monitor

the change in temperature of the system while allowing the reaction to
proceed to determine the value for the enthalpies. This technique, also
known as coffeecup calorimetry, is often used for solutions and phase
transitions, as well as for acidbase reactions.
Differential Scanning Calorimetry: In this process, the sample of
interest is heated slowly alongside a reference solution. Often used to
study biopolymers, we can observe the endothermic protein denaturation through the absorption of heat. By plotting the specific heat
capacity of each sample and finding the area under the curve through
integration, the enthalpy of denaturation can be calculated. By understanding the differences between the reference and the substance of
interest, we can then assess characteristics of each polymer, such as
temperatures of denaturation and the stability of the proteins. 1

Calculations

The following table lists the data recorded for the calorimetric analysis of
each substance of interest:
mass
volume of water
T
Urxn

Benzoic Acid: Smartie:

1.0099 g
.9554 g
2,000 mL
2,000 mL
2.47 K
1.57 K
3124
123432

The energy for this combustion of benzoic acid can be calculated using the
molar energy of combustion,
Urxn

mBA
Urxn
MBA
1.0099 g
=
3227.
122.1213 g

kJ
mol

= -26.68 kJ.
This value can be used to determine the heat capacity of the bomb calorimeter, through the relation defined by the first(?) law of thermodynamics,
Urxn + CV,bomb T +

mwater
CV,water T = 0.
Mwater

Rearranging this equation, we solve for CV,bomb ,

2

(
CV,bomb

mwater
CV,water T + Urxn )
Mwater
.
T

Using density and the known volume to find the mass of the water,
2, 000 ml 0.99704 cmg 3
75.38 molJ K 2.57 K + 26.68kJ)
g
18.0153 mol
=
2.57 K
= 2.04 kJ
K
(

Using this value, we can calculate Urxn .

Urxn

mwater
CV,water T ).
Mwater
2, 000 ml 0.99704 cmg 3
1.31 K+ (
75.38 molJ K 1.31 K ).
g
18.0153 mol

= ( CV,bomb T +
= ( 2.04

kJ
K

= 13.60 kJ
We can convert this value into calories,
13.60 kJ

1000 cal
1 Cal

= 3.25 Cal.
4.184 kJ 1000 cal

Then use the results of the sample to find a value for the caloric content of
a single serving,
3.402 Cal
7g
3.25 Cal
=

= 23.82 Cal/serving.
0.9554 g
g
serving
This calculated value can be compared to the value reported by the bomb
calorimeter, 3412.2. cal/g, which corresponds to 23.89 Cal/serving.
The experimental results agree with the reported nutritional information of
smarties, which reports 25 Calories per serving, for which each serving is 7
grams. A percent error of 4.72% indicates the accuracy of the experiment.
The small discrepancy between the expected and experimental value may be
attributed to the precision of the reported mass or calories per serving.

References
[1] Chang, R. Physical Chemistry for the Biosciences, 1st ed.; University
Science Books, 2005.