EXERCISE 5

Ethalpies of Reaction

EXERCISE 6

Energies of Reaction
 INTRODUCTION

At the end of fifth exerciese, the students are expected to determine the heat of comvustion of the
salicylic acid and acetylsalicylic acid; determine the enthlapy of formation of acetysaliciylic acid using
Hess’s law; and calculate the enthlaphy of reaction of the synthesis of aspirin using the obtained heat of
combustion anf tenthalpu of formation values. Meanwhile, for the sixth exercise, the students should be
able to crete a molecular structures of the species involved in an isodesmic reaction using Avogadro;
generate input files for geometry optimization; perform geometry optimization runs using GAMESS;
calculate the energy of reaction using the total energies of the species; and compare the calculated
value with the literature value.

MATERIALS AND METHOS

Bomb calorimeter experiment was d supposedly done for exercise 5. But due to equipment
malfunctions, data were only provided for computation. Theoretically bomb calorimetry is done by
initially preparing the sample and changing the oxygen bomb as instructed in its manual for use paying
close attention to every details to minimize the errors in the experiment. Next, the calorimeter bucket
was filld with 2000+0.5 grams of distilled water. The bucket was then set in the calormiter. Two ignition
lead wires were pushed into the terminal sockets on the bomb head with the wires orientes araw from
the stirrer shaft. The bomb was lowered completely into the water with its deet spanning the circular
boss in the bottom of the bucket. Then, the handle was then lifted while shaking drops of water back
into the bucket. Finally, the caolrimeter cover was then closed.

After intiating the test, the samples’ wweight and sample ID were inputed. The test started as signaled
bu the PRE-PERIOD light and the short beeps. When the firing was done inside, the post light signaled
that it was done. The cover was opened once the button done was pressed. The bucket containing the
bomb was then removed. After this, the knurled valve knob was slowly opened to reslease the residual
gas pressure. Th cap was the unscrewed and lifted out of th ecyllinder placing on a support stand. The
interior surfaces of the bomb was the washed.The unburned pieces of th efuse were removed and
measured. The length in centimeters was subtracted from its intial length of 10 and multiplied by 2.3
calories per centimeter to obtain the fuse correction.

RESULTS AND DISCUSSION

Table 5-1. Literature Values

Parameter Value
Cp of water, cal/g °C 1
ΔcomH° of benzoic acid, KJ/mol -3226.6
ΔcomH° of acetic acid, kJ/mol -876.1
ΔcomH° of acetic anhydride, kJ/mol -1807.1
ΔcomH°of salicylic acid, kJ/mol -3025
ΔcomH° of acetyl salicylic acid kJ/mol 3926.71
ΔfH° of H2O , kJ/mol -285.6
ΔfH° of CO2 kJ/mol -393.5
ΔfH° of acetic acid kJ/mol -483.5
ΔfH° of acetic anhydride kJ/mol -625.0

Table 5-2 Data on the determination of calorimeter constant (ER) using benzoic acid
Parameter Value
Mass of sample, g 0.4528
Length of unburnt fuse wire, cm 10
2.40
Initial temperature, °C 26.1342
Final Temperature, °C 27.5611
e1, cal -
e2, cal -
ΔT, °C 1.4269
e2, cal 17.48
Δng, moles -0.5
EE, cal °C -193.1851058

Table 5-3. Data on the determination of enthalpies of combustion (ΔcomH) of salicylic acid and
acetylsalicylic
Parameter Value
Salicyclic acid Acetyl salicyclic acid
Mass of sample, g 0.19112 0.9724
Length of unburnt fuse wire, cm 1.16 1.14
Initial temperature, °C 27.8156 28.1381
Final Temperature, °C 29.9135 30.2567
e1, cal - -
e2, cal - -
ΔT, °C 2.0979 2.1186
e2, cal 20.332 20.378
Δng, moles 0 0
ΔcomH°, kJ/mol -2391.062361 -2951.47847
Table 5.4 Calculated molar enthalpies of formation (ΔfH°).

Substance ΔfH, kJ/mol

Acetic Acid -483.5
Acetic anhydride -625
Acetyl salicylic acid -1733.252156
Salicylic acid -1220.833639

Table 5.5 Comparison of the experimental and theoretical ΔrxnH for the synthesis of acetyl salicylic acid
Parameter Value
Experimental ΔrxnH, kJ/mol -370.914514
Theoretical ΔrxnH, kJ/mol -29.29
%Error 1166.35208645%

Table 5.5 Comparison of the experimental and theoretical ΔcomH of salicylic acid and acetyl salicylic acid.

Parameter Value
Salicylic acid Acetyl salicylic acid
Experimental ΔcomH, kJ/mol -2931.062361 -2951.447847
Theoretical ΔcomH, kJ/mol -3025 -3926.71
%Error 20.95661617% 24.83662285%

Table 6.1 Thermodynamic data for organic compounds at 298 K

Compound ΔH (kJ/mol)
Ethene +52.26
Propane -103.85
Ethane -84.68
Propene +20.42

Table 6.2 Total energies calculated using GAMESS

Compound Total Energy (Hartree/molecule) Total Energy (Juoles/molecule)

Reactants
Ethene -78.0306925404 -204808719.3
Propane -118.25969690825 -310398591.7
Products
Ethane 79.2255417243 -208944863.9
Propene 117.06871667445 -307272602

Table 6.3. Enthalpy calculated using GAMESS.

Compound Enthalpy (Juoles/molecule)

Reactants
Ethene -204808719.3
Propane -310398591.7
Products
Ethane -208944863.9
Propene -307272602
Table 6.4 Percent Error

Parameter Value
Calculated ΔH from GAMESS, kJ/mol -10.15491077
Literature ΔH, kJ/mol -12.67
%Error 19.85074373 %