EXERCISE 5

ENTHALPIES OF REACTION

Umerez, Ruth B.

I. Introduction

Standard reaction enthalpy, , is the change in enthaply, a thermodynamic quantity

equal to the total heat content of the system, when reactants in their standard states change to
products in their standard states. There are different forms of reaction enthalpy. They have special
names and a particular significance. Enthalpy of fusion, , is the enthalpy associated with the phase
change from solid to liquid; enthalpy of vaporization, , for liquid to gas; and, enthalpy of
sublimation, , for solid to gas. Consider the reaction:

The standard enthalpy of this reaction is based on the expression

where the terms on the right are the standard molar enthalpies of the products and reactants weighted
by the stoichiometric coefficients in the chemical equation. For the above reaction,

where is the standard enthalpy of formation, change in enthalpy when one mole of a substance in
the standard state is formed from its pure elements under the same conditions, of a certain species at
the temperature of interest.

Standard enthalpy of combustion, , is the standard reaction enthalpy for the complete
oxidation of an organic compound to carbon dioxide and water if the compound contains C, H, and O
and to nitrogen and sulfur dioxide if N and S are present, respectively.

The standard enthalpy of combustion is based on the expression

The focus of the exercise will be on these two: standard enthalpy of formation and
combustion. The latter can be determined by burning a known amount of the substance in a bomb
calorimeter, a sealed vessel which can be pressurized with oxygen. The rise of temperature will then
be measured.

Hess' law states that the enthalpy change of any process equivalent to the successive
carrying out of two other processes is equal to the sum of the enthalpy changes of those two
processes. Given this, standard enthalpies of individual reaction can be combined to obtain the
enthalpy of another reaction.

In the exercise, standardization has been conducted in order for the process to conform to
the standard.

At the end of the exercise, the students should 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' law, and to calculate the enthaply of reaction of the synthesis of aspirin
using the obtained heat of combustion and enthalpy of formation values.

II. Materials and Methods

Figure 5.1. An Adiabatic Bomb Calorimeter

The sample was prepared and the oxygen bomb was charged. Bomb was placed with
0.80-1.00 grams pelleted sample in the fuel capsule. It was placed in the electrode loop. Bomb head
was set on the A38A support and was fastened a 10-cm length of fuse wire between the two
electrodes with the ends of the wire inserted into the eyelet at the end of each stem. Cap was pushed
downward for the wire to be pinched into place. Wire was bent downward toward the surface of the
charge. Sample was placed from bomb head to bomb cylinder. Seal ring was checked and was
moisten with water to freely slide into the cylinder. The head was slid into the cylinder was pushed
down. Gas-release valve was left open and screw cap was set on the cylinder. Gas-release valve was
closed on the bomb head. The hose was connected to a bomb inlet valve. The oxygen button was
pushed on the calorimeter control panel. Forty seconds were needed for the bomb to be filled. The
coupling was disconnected and combustion was proceeded.

The calorimeter bucket was filled with 2000 grams of distilled water. Bucket was set in the
calorimeter. Lifting handle was attached to the two holes in the side of the screw cap. Bomb was
partially lowered in the water. Two ignition lead wires were pushed into the terminal sockets on the
bomb head. Wires were oriented away from the stirrer shaft. Bomb was completely lowered into the
water with its feet to the circular boss in the bottom of the bucket. The lifting handle was removed and
any water drops was shaken back into the bucket. The calorimeter cover was closed with the stirrer
and thermistor probe lowered into the bucket.

Start key or shift start was pushed for test initiation. A number for sample identification was
entered. The weight if the sample was entered. The calorimeter was allowed to conduct the test. The
post light was seen once the bomb has been fired. The done key was pressed for the test result in the
memory of the calorimeter to be stored. The bucket with bomb was removed and the knurled valve
knob on the bomb was opened for residual gas pressure release. The cap was unscrewed and was
placed on the support stand. All interior surfaces of the bomb was washed. Unburned pieces of fuse
wire from the bomb electrodes were removed and was measured. Calorimeter was turned off at the
end of the testing period.

The enthalpies of formation of all substances using their enthalpy of combustion were
calculated which was used for enthalpy of reaction calculation. Literature enthalpy of combustion
values of acetic acid and anhydride and experimental for salicylic and acetylsalicylic acids were used.

III. Results and Discussion

Bomb calorimeter is a closed system vessel that contains bomb that can withstand high
pressure with valves for oxygen addition and electrical contacts for initiating combustion reactions
measuring the heat of combustion of a particular reaction. It is composed of combustion bomb where
the sample undergoes the combustion process. The bucket holds the bomb with a certain water
quantity along with the stirrer for thermal equilibrium. Adiabatic wall protects the bucket from transient
thermal stresses during the combustion. A thermistor observes the changes in temperature while
ignition wires attached to the electrodes initiates the reaction. The general principles in a calorimetry
is a chemical reaction takes place inside the bomb containing the sample to be analyzed with
sufficient oxygen for complete combustion. The bomb is submerged in a bucket of water, and ignition
wires start the combustion. No work is done by the reaction;thus, all the energy will be released as
heat since the reaction takes place in a closed system. It measures the heat release of the reaction
from internal energy which will be coverted to enthalpy.

The energy equivalent or heat capacity of the calorimeter must first be determined which
represents the sum of the heat capacities of the components in the calorimeter. The standardization
process must be executed under a specific operating conditions every time. This is done by burning a
stadard sample, benzoic acid, with a known heat of combustion.The advantage of this is that it is
applicable for samples with ignition difficulties and those with complex combustion mechanism yielding
similar combustion products. To get the energy by the calorimeter, the heat of combustion applied to
benzoic acid is multiplied to the weight of the sample burned, then divided by the temperature rise. On
the other hand, the disadvantages are the standard sample must be available in pure form, stable and
not water absorbing. The sample used in bomb calorimeter is pelletized to make sure that the entire
sample will combust.

The experimental enthalpy of combustion of salicylic and acetylsalicylic acid was

calculated using the following formula:

The first term correlates to the energy absorbed by water which consists of specific heat of water,
molar mass, and change of temperature while the second term is to the energy absorbed by the
calorimeter. This comprises of the molar mass and mass of the sample multiplied to the sum of the
calorimeter constant, and change in moles multiplied to constant R and T final, and fuse wire
correction with formula:

The calorimeter constant was obtained from the standardization of benzoic acid which is 2627.55 .
Since there is sulfur and nitrogen are not present in the combustion, the e and e are both
equal to zero. Based on the balanced reaction of salicylic and acetylsalicylic acids, the number of
moles is 1:1; hence, the change in moles is equal to zero as well. The enthalpy of combustion of
salicylic and acetylsalicylic acid are -3350.063999 and -3275.716977. respectively.
 The combustion reaction of acetylsalicylic acid can be expressed with the equation:

The standard enthalpy of the reaction can be calculated based on the expression:

This is equal to the enthalpy of combustion of acetylsalicylic acid; thus, by manipulating the
expression, enthalpy of formation of the species:

Literature values for the enthalpy of formation of water and carbon dioxide given in Table 6.1 were
subsituted. Since oxygen is in its standard state, the enthalpy of formation is equal to zero.

The same is done with salicylic acid. The combustion reaction and expression for standard
enthalpy of reaction are as follows:

The enthalpy of formation of salicylic and acetylsalicylic are -261.836001. and

-1488.983023. .

The overall reaction can be expressed with the equation:

The standard enthalpy of the reaction can be calculated based on the expression using
Hess' Law:

The calculated enthalpies of formation for acetylsalicylic and salicyclic acid and literature values for
the enthalpies of formation of acetic acid and acetic anhydride in Table 6.1 were used. The calculated
experimental enthalpy of reaction is -1005.647022. . The theoretical enthalpy of reaction, -29.29.
, was computed as well, using the expression for enthalpy of combustion given by:

Literature values for the enthalpy of combustion of acetic acid and acetic anhydride in Table 6.1 were
used.

Given the literature values in Table 6.1, percent errors were considered for the standard
enthalpy of combustion of acetylsalicylic and salicylic acid whose values are -16.57858673% and
10.74591732%, respectively. Percent error for the experimental and theoretical enthalpy of reaction
was 3333.41421%.

Industries make used on the needed or released energy to determine the most effective
method in their production. In food industry, calorie content is equivalent to the amount of energy
released by a body breaking down glycosidic bonds in the food. It s widely utilized in fuel burning
industries such as car companies for example must see how much energy the engine uses or
produces when it burns gasoline for efficient energy choices; thus, saving money. A recent journal
article presented a new way, matrix representation method, of calculating the enthalpy of reaction
through the use of computer via computer language. The thermochemical equation used is as follows:

where n is based on the reactions stocihiometric number matrices; s, the path matrix, is the
occurrence of these reactions resulting to the net equation, n. . The enthalpy of reaction can then be
calculated by the multiplcation of path matrix, s, by the columns matrix of DrH°. In comparison, the
method applied in the exercise is where chemical reaction heats a quantity of water in an insulated
contain. Temperature changes are accounted for along with physical quantity of water, heat capacity,
and mass. It measures the heat release of the reaction from internal energy which will be coverted to
enthalpy.

https://pubs.acs.org/doi/pdfplus/10.1021/ed077p185

IV. Summary and Conclusions

Bomb calorimeter is a closed system vessel that contains bomb that can withstand high
pressure with valves for oxygen addition and electrical contacts for initiating combustion reactions
measuring the heat of combustion of a particular reaction. It is composed of combustion bomb where
the sample undergoes the combustion process. The bucket holds the bomb with a certain water
quantity along with the stirrer during the combustion. A thermistor observes the changes in
temperature while ignition wires attached to the electrodes initiates the reaction. The general
principles in a calorimetry is a chemical reaction heats a quantity of water in an insulated contain.
Temperature changes are accounted for along with physical quantity of water, heat capacity, and
mass. It measures the heat release of the reaction from internal energy which will be coverted to
enthalpy.

Standard reaction enthalpy, , is the change in enthaply, a thermodynamic quantity

equal to the total heat content of the system, when reactants in their standard states change to
products in their standard states. Standard enthalpy of formation, change in enthalpy when one mole
of a substance in the standard state is formed from its pure elements under the same conditions, of a
certain species at the temperature of interest. Standard enthalpy of combustion, , is the standard
reaction enthalpy for the complete oxidation of an organic compound to carbon dioxide and water if
the compound contains C, H, and O and to nitrogen and sulfur dioxide if N and S are present,
respectively.Hess' law states that the enthalpy change of any process equivalent to the successive
carrying out of two other processes is equal to the sum of the enthalpy changes of those two
processes. Given this, standard enthalpies of individual reaction can be combined to obtain the
enthalpy of another reaction.

The enthalpy of combustion of salicylic and acetylsalicylic acid are -3350.063999 and
-3275.716977. ,respectively while their enthalpy of formation are -261.836001. and
-1488.983023. , repsectively. The calculated experimental enthalpy of reaction is -1005.647022.
while the theoretical enthalpy of reaction, -29.29. . Given the literature values in Table 6.1,
percent errors were considered for the standard enthalpy of combustion of acetylsalicylic and salicylic
acid whose values are -16.57858673% and 10.74591732%, respectively. Percent error for the
experimental and theoretical enthalpy of reaction was 3333.41421%.

Industries make used on the needed or released energy to determine the most effective
method in their production. In food industry, calorie content is equivalent to the amount of energy
released by a body breaking down glycosidic bonds in the food. It s widely utilized in fuel burning
industries such as car companies for example must see how much energy the engine uses or
produces when it burns gasoline for efficient energy choices; thus, saving money.

V. Sample Calculations

(refer to the Postlab Notebook)

VI. Literature Cited