EXERCISE 5

ENTHALPIES OF REACTION

CHEM 111.1 – 7L
GROUP 2

GUERRERO, MARY JUSTINE A.

MARQUEZ, RENNARD
PRUDENCIO, DANIEL ANDRE
QUITAIN, CINJALEE
SANGALANG, MARIANE FRANCES

DATE PERFORMED
MARCH 16, 2018

DATE SUBMITTED
MARCH 23, 2018

SUBMITTED TO: SIR PAUL LLOYDSON J. ALVAREZ

 I. Introduction
Enthalpy (H) is a property used to describe the thermodynamics of chemical and
physical processes. It is defined as the sum of a system’s internal energy (U) and the
mathematical product of its pressure (P) and volume (V). It can be expressed as:
H=U + PV [eqn. 5-1]

Enthalpy is considered a state function, since it is derived from three state functions (U,
P, and V). The direct measurement of the enthalpy values for specific substances cannot be
done, only the enthalpy changes for chemical and physical processes can be obtained (Flowers,
2012). Like any other state function, the change in enthalpy (ΔH) between any pair of initial and
final states is independent of the path between them. Normally, changes in enthalpy are
reported for processes taking place under a set of standard conditions. The standard enthalpy
change (ΔH°) is considered the change in enthalpy when reactants in their standard states
change to products in their standard states. It is defined by:

pure, separate reactants in their standard states → pure, separate products in their standard states

The standard enthalpy (ΔH°) of the reaction is expressed as:

Δ rxn H °=∑ v H ° f ( products )−∑ v H ° f ( reactants ) [eqn. 5-2]
where the right-hand side of the equation is the standard molar enthalpies of the products and
reactants multiplied by their respective stoichiometric coefficients (v) in the chemical equation.

Consider the reaction: 4 A + B→ 5 C+2 D

Its standard enthalpy of reaction is:

Δ rxn H °=(5 Δ f H́ ° ,C +2 Δ f H́ ° ,D )−( 4 Δ f H́ ° , A + Δ f H́ ° ,B ) [eqn. 5-3]

where Δf H́ ° is the standard molar enthalpy of formation of the species at the temperature of
interest.

Almost all of the enthalpies of reactions in standard states have special names and a
particular significance. An example of which is the standard enthalpy of combustion (Δcom H́ °). It
is the standard reaction enthalpy for the complete oxidation of an organic compound to carbon
dioxide gas and liquid water if the compound contains C, H, and O, and to N 2 and SO2 gas if N
and S, respectively are also present (Atkins, 2006). It is defined as:
organic cmpd+b O2 ( g) → c H 2 O( l) +dC O2 (g)
In the determination of the heat of combustion of an organic substance a bomb
calorimeter can be employed (Garland, 2009). A bomb calorimeter is a sealed vessel that can
be pressurized with oxygen gas in which the rise in temperature can be measured.
The standard enthalpy change expression is guided by the Hess’ Law, which states that
“the standard enthalpy of an overall reaction is the sum of the standard enthalpies of the
individual reactions into which a reaction may be divided.” Hence, the enthalpy of another
reaction can be obtained from the combination of the standard enthalpies of individual reactions
(Atkins, 2006).
At the end of the experiment the students must be able to determine the heat of
combustion of salicylic acid and acetylsalicylic acid, to determine the enthalpy of formation of
acetylsalicylic acid using Hess’s Law, and to calculate the enthalpy of reaction of the synthesis
of aspirin using the obtained heat of combustion and enthalpy of formation values.

II. Materials and Methods

A Parr 1351 Bomb Calorimeter was employed in the experiment. The experimental set-up is
shown below:

A. Thermistor
B. Stirrer
C. Ignition Wires
D. Adiabatic Wall
E. Combustion Bomb

Figure 5.1. Schematic drawing of an adiabatic bomb calorimeter.

The reagents, salicylic acid and aspirin (acetyl salicylic acid), and the standard, benzoic
acid, were initially weighed. The three were pelleted, then weighed again, having masses of
0.8928 g, 0.8985 g, and 0.8429 g respectively. Afterwards, the bomb calorimeter was charged
by separately placing the pelleted samples in the fuel capsule and then placing it in the
electrode loop. The bomb head was then set on the A38A support and a 10-cm fuse wire was
fastened between the two electrodes by inserting each end of the wire into the eyelet at the end
of each stem of the bomb head. Subsequently, the cap was pushed downward to pinch the wire
into place. The wire was then bent downward towards the surface of the charge. Afterwards, the
bomb head was carefully moved from the support stand to the bomb cylinder. The head was
pushed down (without twisting) and the gas-release valve on the bomb head was left open
during the operation. The screw cap was set on the cylinder and was turn down firmly to a sold
stop. The gas-release valve was then closed. The hose was connected to the bomb inlet valve
and the O2 button on the calorimeter control panel was pushed. The bomb was charged for
approximately 40-s to completely fill it.
After filling the bomb with O2, the calorimeter bucket was filled with 2000 ± 0.5 g
(approximately 2L) of distilled water. The bucket was then set inside the calorimeter. The lifting
handle was attached to the two holes in the side of the screw cap and the bomb was partially
lowered in the water. The two ignition lead wires were then pushed into the terminal sockets on
the bomb head in an orientation were the wires were away from the stirrer shaft. 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 then removed and drops of water were shaken back into the
bucket. The calorimeter was then closed.
In the control panel of the calorimeter, the start button was pushed. The calorimeter was
prompted for the Sample Identification Number. was then entered. The calorimeter prompted
for sample weight. Afterwards, the calorimeter had taken over and conducted the test. The
Done button was pressed after the POST light had appeared. The cover was then opened to
remove the bucket containing the bomb. After removing the bomb from the bucket, the knurled
valve knob on the bomb was slowly opened to release the residual gas pressure. The cap was
unscrewed; the head then was lifted out of the cylinder and was placed on the support stand. All
interior surfaces of the bomb were washed. All the unburned pieces of fuse wires were removed
from the bomb electrodes. The fuse wires were then straightened, and their combined lengths
were measured. After the test, the calorimeter was turned off.
III. Results and Discussion
Enthalpy, frequently regarded to as the heat of the chemical reaction, is the quantity of
heat evolved or amount of energy possessed by a thermodynamic system when a given
quantity of the reaction takes place as represented by its chemical reaction. The direct
measurement of the enthalpy values for specific substances cannot be done, only the enthalpy
changes for chemical and physical processes can be obtained (Flowers, 2012).
The enthalpy changes or any energy change associated with chemical reaction can be
measured through calorimetry. Calorimetry is the study of heat transfer during physical and
chemical processes (Atkins, 2006). In the experiment, the principles in constant-pressure
calorimetry is used in determining the changes in enthalpy (heats of reactions) for reactions
occurring in solution (Zumdahl, 2007).
In the experiment, a Parr bomb calorimeter was employed to measure the energy
transferred as heat. The bomb calorimeter consists of a high-pressure cell, which is regarded to
as the bomb. It is constructed in two parts, a cylindrical body and a headpiece, which are held
together by a large threaded cap. A needle valve or check valve is provided at the top for filling
the bomb with oxygen. It contains a pair of electrical terminals in which a fixed length of fine iron
wire in contact with the pelleted sample is attached (for the experiment, 10 mm of iron wire was
used). The electrical ignition of this wire provides the means of initiating combustion of the
sample, which burns in a small metal pan. It is essential that the wire is in contact with the
sample only so that the actual length of the wire needed to combust the sample can be
measured. The bomb sits in a calorimeter pail containing 2 L of distilled water. Projecting
downward into this pail is a motor-driven stirrer and a precision thermometer. (Garland, 2009).
The water is stirred until a steady or steadily changing temperature is attained, as measured by
the thermometer in the water. The change in temperature, ∆T, of the calorimeter is proportional
to the heat that the reaction releases or absorbs. The conversion of ΔT to heat absorb or
released by the system is best achieved by calibrating the calorimeter using a process of known
energy output and determining the calorimeter constant (Atkins, 2006). There is a variation to
the heat energy required for a substance to change temperature. The heat capacity (C) is the
property at which this is measured. It is defined as heat energy required to raise its temperature
by one degree (Zumdahl, 2007). With the knowledge of the heat capacity of the calorimeter, the
amount of heat transferred to the calorimeter can be calculated. This heat capacity is very
nearly independent of temperature so that:
q=−q cal=−Ccal ΔT [eqn. 5-4]
Since the water is stirred continuously and it does not attain its final temperature
instantaneously, extrapolation techniques are used to determine ΔT. Because the system is at
constant volume (dV=0), there is no work done on and by the system.

W =∫ PdV =0 [eqn. 5-5]

Thus,
ΔU =Q [eqn. 5-6]
The system is designed with an adiabatic jacket. It is used for the it to have the same
temperature as the calorimeter pail, containing the bomb and the water. The water is circulated
through a jacket surrounding the pail and its temperature is automatically controlled to match
that of the calorimeter pail. The adiabatic jacket ensures that the adiabatic conditions for the
reaction is met, since it prevents the escape of heat out of or into the pail through conduction or
radiation. The use of an adiabatic jacket should in principle eliminate the need to plot and
extrapolate temperature values. However, there are inevitable errors in adjusting the jacket
temperature during a run, and the adiabatic jacket on the Parr is more for convenience in
routine. work than for high accuracy. It is also possible to operate the calorimeter without
controlling the temperature of the adiabatic jacket (Garland, 2009).
Before a material with an unknown heat of combustion can be tested in a bomb
calorimeter, the energy equivalent (EE) or heat capacity of the calorimeter must first be
determined. The value of the energy equivalent represents the summation of the heat capacities
of the components in the calorimeter, notably the metal bomb, the bucket, the water in the
bucket and the jacket. Since the system changes slightly with use, energy equivalents are
determined empirically at regular intervals by burning a sample of a standard material with a
known heat of combustion under controlled and reproducible operating conditions. The process
of which a standard of known amount of heat is combusted is referred to as the calibration of
the bomb calorimeter, more commonly known as the standardization. The standardization
produces the energy equivalent of the calorimeter for a specific temperature rise. Standard Test
Methods have been written, tested, and published by a number of international standards
organizations including the American Society for Testing and Materials (ASTM), International
Organization for Standardization (ISO), British Standards Institution (BS), and Deutsches
Institute for Nurmung (DIN). Each of these methods contains procedures for both the initial
standardization and the continuing verification of that standardization. The calibration of the
calorimeters should be calibrated with accordance with the details shown in the test method
used (Parr Instrument Company, 2008).
The bomb calorimeter can be standardized fundamentally by means of electrical
heating, the radiation correction being important, but more commonly it is standardized under
actual working conditions by runs made on standard samples of high purity, whose heats of
combustion have been established by fundamental electrical standardization. The calorimeter
constant (Ccal) may be measured electrically by passing a constant current, I, from a source of
known potential difference, v, through a heater for a known period of time, t, for then (Atkins,
2006)
q=IVt [eqn. 5-7]
In the experiment, Ccal is determined by burning a known mass of substance that has a
known heat output. With the known heat output, it is simple to interpret an observed
temperature rise as a release of heat (Atkins, 2006). Since we used the Parr bomb calorimeter,
it is recommended to use the standardization presented by Parr Instrument Company. It is
stated in their manual that the average energy equivalent of 10 tests must be determined. For
the energy equivalent to be acceptable, the relative standard deviation of this series of tests
shall be 0.17% or less for 6400, 6300, and 6200 cal, 0.34% or less for 6100 cal, 0.50% or less
for 1341 cal and 0.67% or less for 6725 cal. In the event that these criteria are not met, the
source of the problem must be found and corrected, and the entire series repeated until an
acceptable energy equivalent is determined (Parr Instrument Company, 2008). By international
agreement in the 1920’s, benzoic acid was selected as the chemical standard to be used in
calibrating bomb calorimeters. Until today, it remains as the sole chemical primary standard for
this type of calibration since it satisfies the desired properties of a chemical standard. It has the
following properties: readily available in pure form, stable, not hygroscopic, not volatile, easily
brought into a form suitable for combustion, no unusual difficulties during combustion in the
bomb, has complete combustion and the value for the heat of combustion is characterized with
suitable accuracy (Parr Instrument Company, 2008).
Before combustion, the samples (salicylic acid and aspirin) and standard (benzoic acid)
were initially pelletized in the experiment. This process is done to obtain a restricted burning
rate and a complete combustion. It is also done to prevent the sample particles from going to
the exhaust valve. This may cause explosion of the bomb calorimeter. Hence, loose samples
must be contained by either pelletization or placing in a combustion bag to avoid this incident
(American Industrial Hygiene Association, 2018).
The process of combustion is the complete oxidation of an organic compound to carbon
dioxide gas and liquid water if the compound contains C, H, and O, and to N 2 and SO2 gas if N
and S, respectively are also present (Atkins, 2006). The chemical equations for the combustion
of the samples were shown below:

For salicylic acid, C 7 H 6 O 3 +7 O 2 →7 CO 2 + 3 H 2 O (l)

( s) (g) ( g)

For aspirin, C 9 H 8 O 4 + 9 O2 → 9 CO2 + 4 H 2 O (l)

(s ) ( g) (g )

The direct measurement of the enthalpy values for specific substances cannot be done,
instead the changes in enthalpy for chemical and physical processes is obtained. The literature
values of the enthalpies of the samples in the experiment is shown below.
Table 5.1. Literature Values.
Parameters Value
Cp of water, cal/g°C 1
Δcom H́ ° of benzoic acid, kJ/mol -3226.6
Δcom H́ ° of acetic acid, kJ/mol -876.1
Δcom H́ ° of acetic anhydride, kJ/mol -1807.1
Δcom H́ ° of salicylic acid, kJ/mol -3025
Δcom H́ ° of acetyl salicylic acid, kJ/mol -3926.71
Δf H́ ° of H2O(l), kJ/mol -285.8
Δf H́ ° of CO2, kJ/mol -393.5
Δf H́ ° of acetic acid, kJ/mol 483.5
Δf H́ ° of acetic anhydride, kJ/mol -625.0

The standard heats of combustion (Δcom H́ °) of salicylic acid and aspirin were calculated
using the data obtained from the standardization of the benzoic acid the bomb calorimeter. The
Δcom H́ ° is defined as:

( EE )( ∆ T )−e1−e2−e3 + ∆ng R T f
∆ com H́ °=−{
1 cal
[( )(
gC
18.016 g
mol )
(∆ T ) + ][ m ]
( MM sample ) } [eqn. 5-

8]
where ΔT is the temperature change, MM as the molar mass of the sample (for salicylic acid,
138.118g/mol; for aspirin, 180.154 g/mol), m as the mass of the sample, EE energy equivalent
or bomb calorimeter constant, e1 is the correction for nitrogen from trapped air which is 0 since
there is no presence of nitrogen, e2 is the correction for sulfur from trapped air which is also 0
since sulfur is absent, e3 is the fuse wire correction which is the difference between the initial
iron wire length and the length of the unburned wire multiplied to 2.3, Δn g is the difference
between the moles of the products and the moles of the reactants of the gases from combustion
reactions, R as the ideal gas constant, and T f as the final temperature (Ti + ΔT). Below are the
calculated values for the determination of the Δcom H́ °.

Table 5.2. Data on the determination of molar enthalpies of combustion (Δcom H́ ) of salicylic acid
and aspirin.
Parameters Value
Salicylic Acid Aspirin
ΔT, °C 1.97508 1.56578
e3, cal 17.825 16.100
Δng, moles 0 0
EE, cal/°C (from benzoic acid) 2387.54

Using the eqn. 5-8 and plugging in the values on Table 5.2., the molar enthalpies of
combustion (Δcom H́ ) of salicylic acid and aspirin can be obtained. Below are the computed
values of Δcom H́ of the samples and their corresponding percent errors in relation to their
literature values (based from Table 5.1.).
Table 5.3. Comparison of the experimental and theoretical Δcom H́ values of acetylsalicylic acid
and salicylic acid.
Parameter Value
Δcom H́ of aspirin, kJ/mol -3122.776493
Δcom H́ of salicylic acid, kJ/mol -3040.882459
% error (acetylsalicylic acid) -20.4734627
% error (for salicylic acid) 0.5250399669

The enthalpy of another reaction can be obtained from the combination of the standard
enthalpies of individual reactions. The principle of the Hess’s law is significant in the calculation
of the values of ΔH which cannot be determined directly in the experiment. It simply states that,
in going from a particular set of reactants to a particular set of products, the change in enthalpy
is same whether the reaction takes place in one step or in a series of steps (Atkins, 2006). To
put it simply, the enthalpy of a given chemical reaction is constant, regardless of the reaction
happening in one step or many steps. The standard enthalpy (ΔH°) of the reaction is expressed
as:

Δ rxn H °=∑ v H ° f ( products )−∑ v H ° f ( reactants ) [eqn. 5-2]

In in the experiment, it is applied in the synthesis of aspirin, salicylic acid and acetic anhydride
reacts and forms acetylsalicylic acid (aspirin) and acetic acid. The reaction is shown below.
C 7 H 6 O 3 +C 4 H 6 O 3 → C 9 H 8 O 4 +C 2 H 4 O2
In the synthesis of aspirin, the following two reaction enthalpy equations may be expressed.

∆ rxn H ° =∆ f H aspirin +∆ f H acetic acid −∆ f H salicylic acid −∆ f H acetic anhydride

∆ rxn H ° =∆ c H salicylic acid + ∆c H acetic anhydride−∆c H aspirin−∆c H acetic acid

Based from Hess’s Law, the ΔrxnH can be computed from the difference of the formation
enthalpies of the products (acetylsalicylic acid (aspirin) and acetic acid) and the formation
enthalpies of the reactants (salicylic acid and acetic anhydride). It is expressed as:

Δ rxn H ° =Δ f H aspirin + Δ f H acetic acid −( Δ f H salicylic acid + Δ f H acetic anhydride ) [eqn. 5-9]
In the experiment, the molar enthalpies of the reaction are calculated using the molar
enthalpy of formation and molar enthalpy of combustion. Using the experimental values of the
molar enthalpies of formation (Δf H́ ) of salicylic acid and aspirin shown in Table 5.4. and the
experimental values of the molar enthalpies of combustion (Δcom H́ ) of salicylic acid and aspirin
shown in Table 5.3. and the literature values of acetic acid and acetic anhydride shown in Table
5.1., the Δrxn H´ ° values for the synthesis of aspirin can be obtained. The Δ rxn H´ ° is shown in
Table 5.5.

Table 5.4. Calculated molar enthalpies of formation (Δf H́ ).

Substance Δf H́ , kJ/mol
Acetylsalicylic acid -1561.923507
Salicylic acid -571.017541

Table 5.5. Calculated Δrxn H´ ° values for the synthesis of aspirin.

Parameter Value
Δrxn H́ °using Δf H́ values, kJ/mol -849.405966
Δrxn H́ °using Δcom H́ values, kJ/mol -849.105966

Enthalpy can be used in a variety of laws and equations. The concept of enthalpies of
reactions is widely applied in the study of food and energy reserves. The thermochemical
properties of fuels and foods are commonly discussed in terms of their specific enthalpy, the
enthalpy of combustion per gram of material. In the food industry, it is more commonly used in
the nutritional aspect. The specific enthalpies of the fuels are needed in the calculation of the
energy needed by the body for sustenance (Atkins, 2006). The change in enthalpy can also be
applied to refrigerators and hand warmers. In refrigerators, the refrigerants, such as Freon, are
evaporated. The enthalpy of vaporization (liquid to gas energy change) is equivalent to the
coldness of the food. As for hand warmers, as you shake the pack, the hand warmers begin to
heat up. Various reactants inside the pack are exposed to air.
In a recent article, a hygrometer is employed for the measurement of the enthalpy
change through the equipment. The hygrometer is used for refrigerant diagnostics. The
temperature change is measured through a heating system by obtaining the difference between
the air temperature entering and exiting the equipment. In cooling, the moisture of the air is
accounted for in the measurement of the dry bulb temperature. A unit of enthalpy replaces the
dry bulb temperature measurement. The refrigeration gauges need not to be pulled out until the
airflow is known and the enthalpy change through the equipment is measured (Falke, 2018).
 IV. Summary and Conclusions

Enthalpy is the quantity of heat evolved or amount of energy possessed by a

thermodynamic system when a given quantity of the reaction takes place as represented by its
chemical reaction. The direct measurement of the enthalpy values for specific substances
cannot be done, only the enthalpy changes for chemical and physical processes can be
obtained (Flowers, 2012). Like any other state function, the change in enthalpy (ΔH) between
any pair of initial and final states is independent of the path between them. The standard
enthalpy change (ΔH°) is considered the change in enthalpy when reactants in their standard
states change to products in their standard states.
Almost all of the enthalpies of reactions in standard states have special names and a
particular significance. An example of which is the standard enthalpy of combustion (Δcom H́ °). It
is the standard reaction enthalpy for the complete oxidation of an organic compound to carbon
dioxide gas and liquid water if the compound contains C, H, and O, and to N 2 and SO2 gas if N
and S, respectively are also present (Atkins, 2006).
Using Calorimetry, which was the study of heat transfers during physical and chemical
processes, molar heat of combustion of salicylic acid and acetylsalicylic acid (aspirin) were
determined. The bomb calorimeter was employed in the experiment. The calculated values for
the molar heat of combustion for salicylic acid and aspirin are 3040.882459 kJ/mol and
-3122.776493 kJ/mol. In relation to their literature values, the percent error of the molar heat of
combustion of salicylic acid and aspirin are 0.5250399669% and -20.4734627 respectively.
The principle of the Hess’s law is significant in the calculation of the values of ΔH which
cannot be determined directly in the experiment. It simply states that, in going from a particular
set of reactants to a particular set of products, the change in enthalpy is same whether the
reaction takes place in one step or in a series of steps (Atkins, 2006). The enthalpy of another
reaction can be obtained from the combination of the standard enthalpies of individual reactions.
The calculated values for the molar enthalpies of formation of salicylic acid and aspirin are
-571.017541 kJ/mol and -1561.923507 kJ/mol respectively.
In the experiment, the molar enthalpies of the reaction are calculated using the molar
enthalpy of formation and molar enthalpy of combustion. The molar enthalpy of the reaction
calculated using molar heat of formation values yielded a value of -849.40596 while the molar
enthalpy of the reaction calculated using molar heat of combustion values yielded a value of
-849.105966.
 V. Literature Cited

American Industrial Hygiene Association. 2018. Oxygen Bomb Calorimeter Failure.

https://www.aiha.org/get-involved/VolunteerGroups/LabHSCommittee/Pages/Oxygen-Bomb-
Calorimeter-Failure.aspx. Date accessed: 03-23-18.

Atkins,P. and J. de Paula. 2006. Atkin’s Physical Chemistry (Eight Edition). W.H. Freeman and
Company New York. pp. 51-54.

Falke, R. 2018. A Deeper Dive Into Airside HVAC System Diagnostics. Contracting Business.
http://www.contractingbusiness.com/service/deeper-dive-airside-hvac-system-diagnostics.Date
accessed: 03-23-18.
Flowers, P., K. Theopold, and R. Langley. 2012. Chemistry. OpenStax. p. 5.3 Entahlpy

Garland, C.W., J.W. Nibler, and D. P. Shoemaker. 2009. Experiments in Physical Chemistry,
Eight Edition. McGraw-Hill Companies, Inc. pp.152-156.

Parr Instrument Company. 2008. Calibration of Oxygen Bomb Calorimeters: Procedures for
standardization of Parr oxygen bomb calorimeters. Moline, Illinois 61265 USA. p. 1.

Zumdahl, S.S. and S.A. Zumdahl. 2007. Chemistry. Seventh edition. Houghton Mifflin Company.
p. 236.