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ENTHALPIES OF REACTION
Custodio, Janin F.
Aguilar, Keno
Bagabay, Reinier Jay C.
Lopez, Stephanie N.
Group No.1
CHEM 111.1 - 6L
I.
Introduction
Standard enthalpy change is determined when the initial as well as final states of a substance
are in their standard states, meaning substances are in their pure form at 1 bar (Atkins, 2006). Standard
reaction enthalpy ( ) is used to describe this for reactive processes. In general, these are the two
ways of expressing enthalpy:
= , ,
(equation 5-1)
= , ,
(equation 5-2)
Where s and s are the standard molar enthalpies of combustion and formation, respectively, of the
said substances; and s are the stoichiometric coefficients of a balanced chemical equation considering
one mole of the substance of interest. When the reaction involved in the synthesis of aspirin is to be
considered:
C7H6O3 + C4H6O3C9H8O4 + C2H4O2
The obtained equations for the standard enthalpy of reaction are:
= (1 ,C9H8O4 + 1 ,C2H4O2 ) (1 ,C7H6O3 + 1 ,C4H6O3 )
(equation 5-3)
(equation 5-4)
(equation 5-5)
In this equation, ,O2 is zero because the substance is element in its reference form (Levine,
2009).
The amount of heat evolved during combustion reaction, C7H6O3 is measured through the use
of bomb calorimeter. It is a device with sealed metal container placed in isolated container in order to
measure heat flows for gases as well as substances that involve combustion reaction. It uses the change
in water temperature in calculating the amount of heat absorbed. Thus, it may be determined using the
equation:
C7H6 O3 = {[(
)(
18.016
()()1 2 3 +
) ] + C7H6 O3 [
C7 H6 O3
]}
(equation 5-6)
where = calorimetry constant, which varies from one calorimeter to the other; = temperature rise;
= molar mass of sample; = mass of sample tested; 1 = correction for N2; 2 = correction for S; 3 = fuse
wire correction; = change in number of moles of gas components; = gas constant; = final
temperature of system.
,C7H6O3 can then be determined using the literature values of ,H2 O and ,CO2 that can be
determined using different books, and the obtained value of C7H6O3 from calorimetry. In determining the
standard molar enthalpies of combustion and formation of C9H8O4, same method applies. Although derived
from combustion reaction and not from the reaction of interest, the values of molar enthalpies of combustion
and formation may be used in for the synthesis of aspirin using Hess Law. The law states that the
standard enthalpies of individual reactions may combined to determine the enthalpy of another reaction
(Atkins, 2006). Using literature values of the molar enthalpies of combustion and formation of C4H6O3 and
C2H4O2, two values that must be significantly the same may be calculated using equation 5-1 and 5-2.
The objective of this exercise are the following: (1) to determine the heat of combustion of salicylic
acid (C7H6O3) and acetylsalicylic acid (C 9H8O4); (2) to determine the enthalpy of formation of acetylsalicylic
acid (C9H8O4) using Hess Law; and (3) calculate the enthalpy of reaction of the synthesis of aspirin using
the obtained heat of combustion and enthalpy of formation values.
II.
A.
B.
C.
D.
E.
Thermistor
Stirrer
Ignition Wires
Adiabatic Wall
Combustion Bomb
The bomb head was carefully moved from the support stand to the bomb cylinder, making
sure that the bent wire still touches the sample. The sealing ring was checked to make sure that
it was in good condition. Then the head was set to slide down into the cylinder and was pushed
down as far as it can. The head was pushed down gently to avoid twisting and the gas-release
valve was left open during the operation. The screw cap was then used to seal the cylinder and
bomb head firmly.
The gas release valve on the bomb head was closed. The whole thing (i.e. the cylinder
and head bomb sealed by screw cap) was lifted using the lifting handle, attached in the hole
located in the side of the screw cap, and placed in the calorimeter bucket which was filled with
approximately 2000 g (2L) of distilled water inside the bomb calorimeter, until there were no
bubbles produced. It was then removed from the calorimeter and freed from water. The hose used
to supply O2 was connected to the bomb inlet valve and the O2 fill button was pressed on the
control panel of the calorimeter. After filling, the coupling was disconnected.
The lifting handle was again used to put it in the calorimeter bucket to place it partially
lowered in the water. The bomb was handled carefully during the whole process so that the
sample will not be disturbed, making sure that the wire still touches the sample. The two ignition
lead wires was pushed into the terminal sockets on the bomb head. The wires were oriented away
from the stirrer shaft so they would not become tangled in the stirring mechanism. The bomb was
lowered completely into the water with its feet spanning the circular boss in the bottom of the
bucket. The lifting handle was removed and any drops of water were shaken back into the bucket.
The calorimeter cover was closed and then the stirrer and thermistor probe were lowered
into the bucket. The START or SHIFT START Key was pressed to finally start the test. When the
calorimeter prompted for the Sample Identification Number by flashing the SAMPLE ID light, a
number was entered to identify a sample. Finally, when the calorimeter prompted for the sample
weight by flashing the WEIGHT light, the weight of the sample was entered. The test was then
performed by the calorimeter itself. During the time it was establishing the initial equilibrium, the
PRE-PERIOD light was lighted. Just before the bomb fired, a series of short beeps were sounded
to warn users to move away from the calorimeter. The students get out of the classroom during
firing and did not handle the bomb immediately after firing. When the bomb has been fired, the
POST light was displayed in the calorimeter. DONE key was pressed to store the results in the
memory of the calorimeter. The cover was opened and the bucket containing the bomb was
removed. The bomb was removed from the bucket and the knurled valve knob on the bomb was
opened to release the residual gas pressure. The cap was unscrewed, the head was lifted out of
the cylinder and was placed on the support stand.
All of the things that comprise the bomb were washed and dried. All unburned pieces of
fuse wire from the bomb electrodes were collected and straightened. Their combined length was
measured in centimeters. In order to compute for the fuse correction, this length was subtracted
from the initial length of 10 centimeters and the resulting burned length was multiplied by 2.3
calories per centimeter .
Acetylasalicylic acid was then used as a sample and the same procedure was performed.
The calorimeter was turned off at the end of all testing periods. And all of the materials
used were cleaned and dried.
III.
Determination of the enthalpy of the reaction of acetic anhydride with salicylic acid in order
to form salicylic acid and acetic acid was done using an adiabatic bomb calorimeter, in this
exercise. Parr bomb calorimeter, a type of constant volume calorimeter, on the other hand was
used in the experiment.
The assurance of having a complete combustion of the sample is a factor to the accuracy
of results. Since the calculation of heat of combustion is based on the exact weight of the sample
combusted, then all of the mass of the sample must contribute to the heat introduced upon
combustion. This is the reason why first thing that was done during the experiment was to pelletize
the sample. When pelletizing of sample was not done and loose powders were used instead, the
gases produced during combustion which are in turbulent behavior may blow the powder sample
out of the sample capsule, and such blown out sample will be extinguised by the cold bomb wall
before they have been combusted completely. Thus, incomplete combustion is highly probable to
happen. Other advantages of using pelletized sample is that it is more safe to use by restricting
buring rates and ease of handling such that none of the weighed sample is lost during careful
preparation. Generally, pelletizing of sample aims to achieve a specific controlled burning rate in
order to increase the temperature slowly, thus gets the optimum performance of the calorimeter.
Therefore, would probably result to complete combustion.
Bomb calorimeter was then used in the experiment proper. This uses the principle wherein
flow of heat from the reaction inside the cylinder to the walls of the metal container to the water
in the bucket. The change in temperature happening in the water is then used in the calculation
of heat that evolved caused by the reaction. As seen in Figure 5.1, the metal combustion bomb,
which is equivalent to the combustion reaction chamber, is immersed in a bucket of measured
amount of water. This chamber maintains a constant volume and allows the heat generated in its
interior to be transferred efficiently to its walls and finally to the surrounding bath (Atkins, 2006).
A stirrer facilitates stirring of the water in the bucket until a steady or steadily changing
temperature is attained, as measured by a thermometer (Mortimer, 2008). Using the fuse wire,
the sample is ignited electrically inside this chamber, which makes the combustion reaction to
occur. The apparatus also consists of an adiabatic wall to prevent heat transfer beyond the water
bath.
The interior of the reaction chamber is pressurized with oxygen in order to ensure
complete combustion of the reaction. This is done before the ignition.
In the determination of heat of combustion of the sample, the general principle used is the
amount of heat transferred to the calorimeter after the combustion reaction (Mortimer, 2008).The
heat produced by the combustion inside the cylinder is equilibrated through the walls of the
cylinder and then into the surrounding water bath, wherein temperature increase can be
determined with respect to the time (Levine, 2009). Therefore, the change in temperature of the
system is proportional to the heat of combustion of the sample (Atkins, 2009). Using the
determined of the system and equation 5-6, heat of combustion can be determined. Through
this experiment, change in temperature can be measured thrpugh the water bath, and thus, this
observed temperature increase must be related to the heat released inside the bomb cell. The
heat transferred is not only caused by the combustion system but the physical parts of the
calorimeter itself also have a contribution (Mortimer, 2008). The error caused by this can then be
avoided by standardization or calibration of the calorimeter.
Substance
Experimental
Molar Enthalpy
of Cumbustion
Theoretical
Molar Heat of
Combustion
Percent
Error
Salicylic acid
-3059.42 kJ/mol
-3025 kJ/mol
1.14%
Acetylsalicylic
acid
-3628.42 kJ/mol
-3957 kJ/mol
8.30%
Inefficient standardization of the calorimeter may have contributed to the errors in the
experimental values since it was not calibrated right before the tests. If there was an incomplete
combustion, the mass that must be used in the calculation must be lower. In the actual calculation,
the mass used is greater than the actual mass the combusted. Since the mass variable is in the
denominator of the term that accounts for Qcal, Qcal becomes less negative, so as the experimental
value of the molar heat of combustion. In this case, a negative percent error must be calculated.
From the table, acetylsalicylic acid seems to have undergone incomplete combustion.
By considering the combustion reaction of a substance, as introduced previously, the
values derived for , and , may be used to determine the
values of , and , . Evaluating Equation 5-5 and extending it
to acetylsalicylic acid, and using literaure values for the enthalpies of formation of carbon dioxide
and water, the following values for , and , are derived.
Enthalpy of Formation
Carbon Dioxide
-393.51 kJ/mol
Water
-285.83 kJ/mol
Table 5.3 . Derived molar enthalpies of formation of salicylic acid and acetylic salicylic acid using
experimentally-determined molar enthalpies of combustion.
Substance
Salicylic acid
-552.64 kJ/mol
Acetylsalicylic acid
363.75 kJ/mol
is:
( equation 5-7)
Enthalpy of Formation
Acetic Acid
-484.50 kJ/mol
Acetic Anhydride
-624.00 kJ/mol
(equation 5-8)
Hess Law is basically the basis of the equality of the two expression. Considering the combustion
reactions of the reactants and products:
Chemical Equations:
C7 H6 O3
C4 H6 O3
C9 H8 O4
C2 H4 O2
In order to come up with the reaction of interest, the third and fourth equations must change
direction, so as the sign of their respective must be negated. Common substances on the
left side of the equation of the same amount on the right side is cancelled. The total is the
sum of the of the individual reactions, in acordance to Hess Law.
Chemical Equations:
C7 H6 O3
C4 H6 O3
- C9 H8 O4
- C2 H4 O2
Because it has been proven that the molar enthalpy of reaction may also be calculated
using molar enthalpies of combustion derived previously. Still, literature values for molar
enthalpies of combustion of acetic anhydride and acetic acid are used.
Table 5.5 Percent difference between using molar enthalpies of formation and
using molar enthalpies of combustion.
Parameters
Value
using molar
enthalpies of formation
363.75 kJ/mol
using molar
enthalpies of combustion
-363.75 kJ/mol
Percent difference
0%
Aside from the procedure used in this experiment, there are still many available
procedures available for determining enthalpies of reaction. One example uses the Setaran hightemperature heat-flux Tian-Calvet microcalorimeter instead of an oxygen bomb calorimeter.
Though it still follows the calorimetric method. The experiment that used this methos specifically
used the melt dissolution calorimetry.This certain method makes use of a transmission spectrum.
(Ogoradova, 2010)
The concept of of enthalpy is not constricted to laboratories, instead it can be applied in
industries. It can be of a great use specifically in the part of energy efficiency analyses. By defining
the enthalpies of formation of the material streams in industrial processes, calculated reaction
energies give more precise energy balance for the reaction processes (Toumalala, 2009).
Another possible application is the way of monitoring the energy content of fuels and foods
through determining the enthalpies of their corresponding useful reactions.
IV.
Bomb calorimeter is of great use in the determination of the change in temperature mainly
caused by the heat combustion of specific substances such as salicylic acid and acetylsalicylic
acid. The information obtained here could then be used in the evaluation of the specific equation
to solve for heat of combustion. These equations take into account the necessary correction
factors for the limitations of the experiment. In the experimental evaluation, the values obtained
for the enthalpies of combustion of salicylic acid and acetylsalicylic acid are -3059.42 kJ/mol and
-3628.42kJ/mol, respectively. These experimental values are acceptable since as to compare to
the literature values, their percent errors are 1.14% and 8.3%. Considering the combustion
reaction of each substance, the corresponding molar enthalpies of formation are determined.
Through Hess Law it is proven that the equation for enthalpy of reaction that is by definition based
on the enthalpies of formation may be equally expressed on a basis of the enthalpies of
combustion of the substances involved in the reaction.
V.
Literature Cited
ATKINS, P. AND DE PAULA, J. 2006. Physical Chemistry. 8th ed. New York: Oxford
University Press.
LEVINE, I.N. 2009. Physical Chemistry. 6th ed. New York: McGraw-Hill.
MORTIMER, R.G. 2008. Physical Chemistry. 3rd ed. London: Elsevier Inc.
OGORODOVA, L.P., KISSELEVA, I.A., MELCHAKOVA, L.V., VIGASINA, M.F. AND
SPIRIDONOV, E.M. 2010. Russian Journal of Physical Chemistry.
PARR INSTRUMENT COMPANY. Parr Bomb Calorimeter Tech Notes: Calibration of Oxygen
Bomb Calorimeters.