Alex Dunsmoor

Marvin Moreland
Chem 333 Sec.2
Date Performed: 9/24/13
Date Turned in: 10/16/13 (re-did lab)

Purpose:

In this experiment, my lab partner and I determined the heat of combustion for

Naphthalene utilizing a bomb calorimeter.

Procedure:

The procedure was followed from pages 152-158 of Experiments in Physical Chemistry

by Garland and Shoemaker, 2009 {1}. Deviations to this written procedure were provided

by Louis Scudiero’s handout “Heats of Combustion Supplement (Bomb Calorimetry){2}.

For our particular experiment, we used an electric thermometer that took temperature

measurements every millisecond. The use of this apparatus also required calibrating the

unit, who’s procedure is given in the supplement{2}. Other deviations included filling the

bomb to 15 atm gauge pressure, not fusing the iron ignition wire into pressed sample but

resting it on top, not purging the bomb with nitrogen after each run, and wiping the inside

of the bomb dry after each run. In terms of operation, we opted for the medium

temperature setting.
 Data:

Table 1 lists the mass of each sample and the iron wire used for each sample. It also lists

the determined initial and final temperatures and times, pre and post combustion

temperature drifts, the drift time divisor value (td), and the adiabatic temperature change.

Table 1

Sample Benzoic Acid 1 Benzoic Acid 2 Naphthalene 1 Naphthalene 2

Pellet Mass (g) 0.7990 0.8039 0.4851 0.4892
Mass Iron Pre Combustion (g) 0.0150 0.0178 0.0181 0.1450
Mass Iron Post Combustion (g) 0.0054 0.0037 0.0052 0.0071
Pre Combustion Drift (°C/ms) -0.0002 -0.0001 0.0000 -0.0001
Post Combustion Drift (°C/ms) -0.0001 0.0004 0.0000 0.0000
ti (ms) 622.2000 279.0000 229.8000 197.2000
Ti (°C) 24.2245 24.8050 24.0151 23.9372
tf (ms) 952.8000 596.4000 559.6000 504.8000
Tf (°C) 26.2345 26.6389 25.8219 25.8028
td (ms) 690.2013 344.5797 295.2752 268.1251
ΔTadiabatic (°C) 2.0353 1.7458 1.8085 1.8764

Table 2 lists the heat capacity of the system with respect to the known energy of

combustion for benzoic acid and iron wire, and the average heat capacity of the system

used for finding the energy of combustion for naphthalene.

Table 2

Sample Benzoic Acid 1 Benzoic Acid 2

C(s) (Kj/K) 18.76 20.58
Average C(s) (Kj/K) 19.67
Table 3 lists the calculated energy and enthalpy of combustion for naphthalene.

Table 3

Sample Naphthalene 1 Naphthalene 2

ΔENaphthalene (KJ) -20.36 -20.30
ΔHcombustion (KJ) -2609.90 -2601.25
ΔHcombustion (KJ/mol) -5380.13 -5317.35

Table 4 lists miscellaneous constants used in the calculations

Table 4

ΔEBenzoic Acid (Kj/g) -26.41

ΔEIron wire (Kj/g) -6.68
Mass of Water in Calorimeter (g) 2000
Cpwater (KJ/mol*K) 0.07535
Molar Mass Water (g/mol) 18.02
Molar Mass Naphthalene (g/mol) 128.17
Molar Mass Benzoic Acid (g/mol) 122.12
Molar Mass Iron (g/mol) 55.845
Gas Constant R (KJ/mol*K) 0.00831
Room Temp at Time of Experiment (K) 296.45

Table 5 compares the calculated heat of combustion to literature values, and gives the

error associated with the measurements

Table 5

Sample Naphthalene 1 Naphthalene 2

Calculated (KJ/mol) -5380.13 -5317.35
Literature (KJ/mol) -5157 -5157
% Difference 4.33 3.11
error (±) 11.917 11.906
Charts 1-4 show the temperature vs time plot, along with the respective pre and post

combustion drifts, final and initial temperature, and drift time devisor.
Calculations:

First, the adiabatic temperature change (ΔT’) is calculated using equation [1]

𝑑𝑇 𝑑𝑇
[1] ∆𝑇 ′ = (𝑇𝑓 − 𝑇𝑖 ) − (𝑡𝑑 − 𝑡𝑖 ) − (𝑡𝑓 − 𝑡𝑑 )
𝑑𝑡 𝑖 𝑑𝑡 𝑓

Where Tf and Ti are the final and initial temperature respectively. These values are taken

as the stable temperatures once the system has reached equilibrium before and after

𝑑𝑇 𝑑𝑇
combustion. and are the temperature drifts before and after combustion
𝑑𝑡 𝑖 𝑑𝑡 𝑓

respectively. ti and tf are the times at which the initial and final temperatures are taken. td

is the drift time devisor.

Next, the heat capacity of the system [C(s)] is figured using equation [2]

(∑𝑛𝑖=1 𝑚𝑖 ∆𝐸𝑖 )
[2] 𝐶(𝑠) = − [ ] + 𝑛𝑤𝑎𝑡𝑒𝑟 𝐶𝑝𝑤𝑎𝑡𝑒𝑟
∆𝑇 ′

Where ∑𝑛𝑖=1 𝑚𝑖 ∆𝐸𝑖 is the sum of the energy of combustions multiplied by their respective

mass for the benzoic acid and iron wire; 𝑛𝑤𝑎𝑡𝑒𝑟 𝐶𝑝𝑤𝑎𝑡𝑒𝑟 is the moles of water surrounding
 the bomb multiplied by its heat capacity at constant pressure. ΔT’ is the adiabatic

temperature change

With the heat capacity of the system figured, equation [2] is rearranged to

equation [3] to solve for the energy of combustion for naphthalene.

[3] ∆𝐸𝑁𝑎𝑝ℎ𝑡ℎ𝑎𝑙𝑒𝑛𝑒 = (𝐶(𝑠)𝑎𝑣𝑔 ∗ 𝑚𝐶10 𝐻8 ) + (𝑚𝐹𝑒 ∗ ∆𝐸𝐹𝑒 ) − (𝑛𝑤𝑎𝑡𝑒𝑟 ∗ 𝐶𝑝𝑤𝑎𝑡𝑒𝑟 ∗ ∆𝑇 ′ )

Where C(s)avg is the average heat capacity of the system; figured by applying equation [2]

to both samples of benzoic acid and taking the average of the results. 𝑚𝐶10 𝐻8 is the mass

of the naphthalene sample, 𝑚𝐹𝑒 is the mass of iron wire burned in the sample.

Finally the enthalpy of combustion (ΔHcombustion) is found using equation [4]

[4] ∆𝐻𝐶𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛 = ∆𝐸𝑁𝑎𝑝ℎ𝑡ℎ𝑎𝑙𝑒𝑛𝑒 + 𝑅𝑇∆𝑛𝑔𝑎𝑠

Where R is the gas constant and ∆𝑛𝑔𝑎𝑠 is the change in moles of gas for reaction [5]
[5] 𝐶10 𝐻8 (𝑠) + 12𝑂2 (𝑔) → 10𝐶𝑂2 (𝑔) + 4𝐻2 𝑂(𝑔)

Error Analysis:

Plugging in all the constituent parts that make up equation [4] gives an equation too long

to be printed legibly. The partial of this equation is taken with respect to T, mn (mass of

naphthalene), mba (mass of benzoic acid), mfe (mass of iron), Tf, Ti, td, ti, Tf. All the errors

associated with these measurements are ±0.0001. Each of the of these partial derivatives

is squared and multiplied by 0.0001 squared. The square root of the sum of all these

factors is taken as the error for measuring ΔH. The result is shown in table 5. The

literature value for the heat of combustion for naphthalene was taken from reference{3}

Discussion:

In the calculations of this experiment, we assumed the ideal gas law was valid; making

the calculations easier. The difference between the magnitude of error from the perfect-gas law

and the experimental uncertainties is quite large. From the propagation of error, the error

introduced by the perfect-gas law was extremely small (close to 10-4 KJ). However, the

uncertainty that lies along with the experimental process and the equipment was much larger

(around 10-1 KJ). This means that assuming the gas within the bomb is perfect will yield less

uncertainty than if the experiment was performed with equipment of similar precision.
 In not knowing the specific heat of Naphthalene, it had to be calculated from a known

substance and compared to a known compound. This represents the first portion of the

experiment and all the uncertainty which comes along with it. The error involved in finding the

specific heat is equal to the total error of everything calculated in this. From the error analysis, it

is found that not knowing the specific heat of naphthalene introduced an error of ±0.516 kJ/K to

the experiment.

The ΔH value pertains to the final temperature because the enthalpy at initial temperature

is taken as the reference in the calculations; so it is zero.

References:

1. Carl W. Garland, Joseph W. Nibler, David P. Shoemaker, Experiments in Physical

Chemistry 8th Ed. McGraw Hill 2003 p.152-158

2. Heats of Combustion Supplement (Bomb Calorimetry) by Louis Scudiero

3. Richard M. Felder, Ronald W. Rousseau, Elementary Principles of Chemical

Engineering 3rd Ed. Wiley 2005 table B.1