GARCIA, Krizzi Eve D.

3CHEM1

I. TITLE:

Calculating for the Heat of Combustion

II. OBJECTIVES:

● To differentiate between different levels of theory (molecular mechanics,

semi-empirical, ab inito and DFT methods)
● To run calculations on a computational chemistry software
● To use computational chemistry to calculate the heat of combustion
organic compounds

III. METHODOLOGY:
In this experiment, the calculation of the heat of combustion was done by
performing computational chemistry. The principle behind this involves the use of
computers in modeling chemical systems to be utilized in the determination and
calculation of a system’s chemical properties.

Figure 1. Optimization of the molecule

 In conducting the experiment, getting familiarized with the tools and features of
the server is of utmost importance since computational chemistry involves the use of
software. Getting a background about the methods used in the computations could
serve as a guide in understanding the concepts of computational chemistry. After
navigating through the webpage, select the option GAMESS. This software lets
customization and setup of various parameters for the molecule being analyzed. In
this case, four compounds are being studied which are octane, butane, butanol and
ethanol. These molecules are typed into the search bar and the molecule chosen
appears on the side. The optimization of the structure occurs consequently.
Afterwards, the parameters were set with the option PM3 selected while all the other
parameters remain unchanged. The option ‘Submit Job’ was selected and the
resulting values were saved. The output file was scanned through to obtain the value
of the heat of formation of the molecule.
Although there are three general steps involving a quantum calculation according
to the software. First, the molecule must be described and the particular calculation
desired must be specified. Second, the calculation is performed (submit a job) by
running a program using the information that was inputted. Lastly, the output is
viewed in a text file format and the optimum x,y,z coordinates are viewed graphically.
This is done by selecting the “Job Status”. Other information about the molecule
such as bond length, bond angle, molecular orbitals etc. as well as IR vibrations can
also be viewed.
The obtained heat of formations for octane, butane, butanol and ethane were
recorded. After obtaining the values, the heat of combustion was calculated using the
heat of formations given for carbon dioxide and water. The heat of combustion was
calculated using Hess’ Law. This equation involves the summation of heats of
formation of the products minus the summation of the heats of formation of the
reactants at standard conditions to yield the enthalpy of combustion. Then the heat
of combustion from the literature was obtained through the NIST. Lastly, the
calculated value was compared to the literature values by calculating for the percent
error for each compound.

IV. RESULTS:

The main objective of the experiment was to calculate the heat of

combustion of the organic compounds octane, butane, ethanol and butanol using
computational chemistry. Also, the different levels of theory were characterized
and described. Understanding of the concepts involved in the methods was
analyzed as well. The GAMESS software was utilized for the calculation of the
desired thermodynamic value. For each compound, the software was allowed to
run for four times.
 A. Octane

Heat of formation = -50.71952 kcal/mol = -212.21 kJ/mol

B. Butane

Heat of formation = -28.70375 kcal/mol = -120.10 kJ/mol

C. Butanol

Heat of formation = -66.28948 kcal/mol = -277.36 kJ/mol

 D. Ethanol

Heat of formation = -56.84916 kcal/mol = -237.86 kJ/mol

V. CALCULATIONS:

In order to interpret the results of the experiment, the principles of the first law of
thermodynamics should be applied. The calculation for the heat of combustion was done by
applying the formula:

Table 1. Results for the determination of the heat of combustion of the

compounds
Fuel/Compound ΔHf (PM3) ΔHc (PM3) ΔHc (NIST) %error

Octane -212.21 kJ/mol -5508.26 kJ/mol -5430 kJ/mol 1.44%

Butane -120.10 kJ/mol -2883.05kJ/mol -2877.5 kJ/mol 0.19%

Butanol -277.36 kJ/mol -2725.79 kJ/mol -2676 kJ/mol 1.86%

Ethanol -237.86 kJ/mol -1406.63 kJ/mol -1366.3 kJ/mol 2.95%

A. Octane
Standard enthalpy of formation of CO2= -393.5 kJ/mol
Standard enthalpy of formation of H2O = -285.83 kJ/mol
Chemical reaction for the combustion of octane:
C8H18(g) + 12 ½ O2(g) → 8CO2(g) + 9H2O(g)

To determine the heat of combustion, an application of Hess’ Law was utilized.

ΔHcomb = 8(ΔHf°CO2(g)) + 9 (ΔHf°H2O(g)) - (ΔHf°C8H18(g)) + 12 ½ (ΔHf°O2(g))
= 8(-393.5 kJ/mol) + 9(-285.83 kJ/mol) - (-212.21 kJ/mol) + 0
= -5508.26 kJ/mol

ΔHcomb theoretical value = -5430 kJ/mol

%error = |experimental value - theoretical value| / theoretical value
kJ kJ
=
|−5508.26 mol −−5430
mol |
x 100=1.44 %
kJ
−5430
mol

B. Butane
Chemical reaction for the combustion of butane:
C4H10(g) + 6 ½ O2(g) → 4CO2(g) + 5H2O(g)

ΔHcomb = 4(ΔHf°CO2(g)) + 5 (ΔHf°H2O(g)) - (ΔHf°C4H10(g)) + 6 ½ (ΔHf°O2(g))

= 4(-393.5 kJ/mol) + 5(-285.83 kJ/mol) - (-120.10 kJ/mol) + 0
= -2883.05kJ/mol

ΔHcomb theoretical value =-2877.5 kJ/mol

kJ kJ
%error =
|−2883.05 mol −−2877.5
mol |
x 100=0.19 %
kJ
−2877.5
mol

C. Butanol
Chemical reaction for the combustion of butane:
C4H9OH(g) + 6O2(g) → 4CO2(g) + 5H2O(g)

ΔHcomb = 4(ΔHf°CO2(g)) + 5(ΔHf°H2O(g)) - (ΔHf°C4H10(g)) + 6(ΔHf°O2(g))

= 4(-393.5 kJ/mol) + 5(-285.83 kJ/mol) - (-277.36 kJ/mol) + 0
= -2725.79 kJ/mol

ΔHcomb theoretical value = -2676 kJ/mol

kJ kJ
%error =
|−2725.79 mol −−2676
mol |
x 100=1.86 %
kJ
−2676
mol

D. Ethanol
Chemical reaction for the combustion of butane:
C2H5OH(g) + 3O2(g) → 2CO2(g) + 3H2O(g)
ΔHcomb = 2(ΔHf°CO2(g)) + 3 (ΔHf°H2O(g)) - (ΔHf°C4H10(g)) + 3(ΔHf°O2(g))
= 2(-393.5 kJ/mol) + 3(-285.83 kJ/mol) - (-237.86 kJ/mol) + 0
= -1406.63 kJ/mol

ΔHcomb theoretical value = -1366.3 kJ/mol

kJ kJ
%error =
|−1406.63 mol −−1366.3
mol |
x 100=2.95 %
kJ
−1366.3
mol
VI. CONCLUSION:

The experiment conducted involved the principles of thermodynamics

specifically the second law. Hess' law is derived from the first law of
thermodynamics which states that energy cannot be created or destroyed but
can be transformed from one form to another. Quantum chemical methods
enable the execution of several equations to be compressed into a relatively
easier and faster method. Using the PM3 method or Parametric Method 3 which
is a semi-empirical method based on the Neglect of Differential Diatomic Overlap
(NDDO) integral approximation. This method allows the quantum calculation of
molecular electronic structure in computational chemistry.
The objectives of the experiment were achieved by utilization of the
GAMESS software where determination of the heat of formation was done
through the data input. The heat of formation obtained was utilized in Hess’ Law
to calculate the heat of combustion which was compared to the reference values
from NIST. The percent error was also calculated afterwards to determine the
degree of deviation from the reference value. Overall, the obtained values have
high accuracy based on the calculated percent error. Thus, computational
chemistry yields high accuracy results in determining the heat of combustion of
substances.