Aaron Reinicker

Nathaly Murillo

Physical Chemistry Laboratory I

CHEM 445-021
Experiment 4: Heat of Combustion

Abstract

The measurement of heats of reactions is tedious and difficult, which is why the

heat of reaction of a compound is usually calculated from the heats of formation of the

components. In this experiment the heat of combustion of biphenyl, (C6H5)2, a relatively

non-volatile organic compound, was determined by means of an adiabatic bomb

calorimeter. The heat capacity of the calorimeter was first calculated combusting a

measured amount of benzoic acid, C6H5COOH, since its heat of combustion is known:

ΔE{Comb, Benzoic acid}= -26.433 kJ/g. The heat capacity of the calorimeter was found

to be 10.49117±0.013 kJ/ºC. The average heat of combustion, ΔrxnH, of biphenyl was

calculated to be -6262.84 + 23.23kJ/mol. The published value in the NIST Webbook for

the enthalpy of combustion of biphenyl is -6250 + 20 kJ/mol, which is within the

experimental value obtained.

Introduction

In this experiment the heat of combustion of biphenyl, (C6H5)2, a relatively non-

volatile organic compound, was determined by means of an adiabatic bomb calorimeter.

Since biphenyl is an organic compound, the sample will burn rapidly and quantitatively

in excess-oxygen forming a distinct product. With the aid of the heats of combustion of

organic compounds, the balanced equation for the reaction (1), and data for the heats of

formation of H2O and CO2, the heat of formation of the compound was determined.

(1) (C6H5)2 + 14.5O2 → 12H2O + 15CO2

The adiabatic bomb calorimeter maintains the change in heat, Q, at zero and at

constant volume. To analyze the data T1and T2 will be measured and used to determine

ΔRxnE by applying them into the following equation 2:

(2) ΔRxnE= -∫Cv {System}dT= -Cv{System}*(T2-T1)

It is assumed that the heat capacity of the system is independent of temperature

due to the small change in temperature. To determine ΔRxnE and Q the heat capacity, CV,

of the system is needed. CV {system} was calculated by adding a known amount of

electrical energy to burn a measured amount of benzoic acid, C6H5COOH, since its heat

of combustion is known: ΔE{Comb, Benzoic acid}= -26.433 kJ/g, and measuring the rise

in temperature. The change in temperature is measured and the heat capacity can be

determined using equation 3:

(3) Cv{System}= ΔCombE{Standard}/ ΔTCorr

The heat of combustion of biphenyl was then determined using the temperature

rise on combustion of the sample and the calculated heat capacity of the system. The

reaction is performed at constant pressure rather than constant volume, therefore the
reaction is most commonly calculated as ΔrxnH rather than ΔRxnE. To convert between the

two, equation 4 is needed.

(4) ΔH=ΔE + RTΔngas

The equation includes the correction term, Δngas, or the increase in moles of gas

resulting from the combustion, since the combustion of biphenyl includes gaseous

components and unlike solids and liquids, it cannot be ignored.

Procedure

In this experiment the Parr Instruments 1341 Oxygen Bomb Calorimeter with an

1108 Oxygen Combustion Bomb and 1672 Calorimetric Thermometer was used to

determine the heat of combustion of biphenyl. For the determination of the heat capacity

of the system, a benzoic acid pellet of approximately 0.9g was used. A hole was made in

the center of the pellet, by passing a hot wire though, so a 10 cm measured, cut, and

weighted length of iron wire could be wrapped around the pellet and attached to the

electrodes of the bomb head assembly. The bomb was then assembled by placing the

bomb head assembly into the casing then seating the rubber gasket seal. Next, the

stainless steel ring was set and the top of the bomb was screwed on. The bomb was the n

filled with oxygen gas to 25atm, the release valve was then opened to allow drop back to

1atm, and finally filled with oxygen gas to 25atm. The bomb was then placed in the dry

polished can, the leads were attached, and 2L of water was then added to the surrounding

insulating jacket. The cover was placed with the stirrer propeller towards the rear, turned

on, and the temperature was then measured for 5 minutes, then the sample was ignited

and data were collected for about 10 minutes until the temperature became constant. The
bomb was then removed from the insulating jacket and taken apart. The weight of the

remaining iron wire was recorded.

This procedure was repeated 3 more times instead of 2 due to data loss. The

determination of the heat of combustion for biphenyl was similar to the procedure for

benzoic acid but instead a pellet of approximately 0.6g of biphenyl was used. The pellet

was made by grinding the crystals in a mortar and pestle and then the sample was placed

in the die and compressed. This procedure was done 3 times in order to obtain an accurate

measurement.

Data and Results:

 Table 1 – Benzoic Acid Data for Determining Cv

Wire Mass Mass of Mass of Wire ∆TCorr ∆ETotal CV{syste

Mass Wire + Benzoic Wire Burned (kJ) m}
(C)
(g) Benzoic Acid (g) Left (g) (g) (kJ/C)
Acid
0.0144 0.9777 0.9633 0.0153 0 2.4260 -25.4629 10.4959
0.0159 0.9721 0.9562 0.0097 0.0062 2.4104 -25.3115 10.5012
0.0163 0.9885 0.9722 0.0134 0.0029 2.4546 -25.7125 10.4764

Cv Standard
Average: Deviation
kJ/C
10.49117 0.013058

Footnotes: ∆E{Comb, Benzoic acid} = −26.433 kJ/g , ∆E{Comb, Fe} = − 5.86 kJ/g

Figure 1

Temperature vs. Time Benzoic Acid

25.5
25
24.5
Temp (C)

24
Series1
23.5
23
22.5
22
0 100 200 300 400 500 600 700 800 900
time (s)

Table 2- Biphenyl Data for Determining ∆Η of the Reaction

 Wire Mass of Wire ∆TCorr ∆Ewire ∆Etotal ∆Etotal RT(∆n) ∆Htotal
Mass (g) Biphenyl Burned (kJ) (kJ) (kJ/mol) (kJ) (kJ)
(C)
(g) (g)
0.0169 0.5862 0.0099 2.2818 -0.0580 -23.8806 -6282.20 -0.0233 -23.9039
0.0158 0.5948 0.0003 2.2789 -0.0018 -23.9061 -6197.98 -0.0237 -23.9298
0.0154 0.5825 0 2.2653 0 -23.7651 -6291.53 -0.0232 -23.7883

Cv ∆Hrxn ∆Etotal ∆Hrxn

Average: Average: Average Average
kJ/C (kJ) (kJ/mol) (kJ/mol)

10.4912 -23.8740 -6257 -6262.84

+ 0.01306 + 0.0887 + 51.53 + 23.23

Footnotes: For ∆Hrxn calculations, T = 295.01K

∆E{Comb, Benzoic acid} = −26.433 kJ/g , ∆E{Comb, Fe} = − 5.86 kJ/g
Average number of moles per trial: 0.003812 moles

Figure 2

Temperature vs Time Trial 1 Biphenyl

25.5
25
24.5
Temperature (C)

24
23.5
Series1
23
22.5
22
21.5
21
0 200 400 600 800 1000
time (s)
Discussion and Analysis:

Table 1 above contains all of the values that were necessary in our calculation of

Cv{system}. This value for Cv was calculated using this equation:

(5)

The corrected temperature value was calculated from the temperature vs. time graph for

each trial at the time when the temperature had increased to 60% of the maximum. In

order to obtain this value, we first had to find an equation for the flat regions of the

temperature vs. time graph, one corresponding to the maximum temperature, the other

corresponding to the minimum temperature. Then we plugged different times into these

equations to find ∆T at each time. The point that had the maximum ∆T corresponded to

the time and calculated 60% of its maximum temperature (∆T*0.6 + Tmin at time t).

Then we found the time corresponding to this 60% maximum temperature and calculated

the ∆T at this point which is ∆Tcorr. ∆E was calculated from the total mass of wire and

benzoic acid burned using these constants:

∆E{Comb, Benzoic acid} = −26.433 kJ/g , ∆E{Comb, Fe} = − 5.86 kJ/g

And used this to calculate the Cv{system} to be 10.49117 + 0.013058 kJ/C. After we

calculated Cv{system}, we were able to calculate ∆E using equation 9:

First we calculated ∆Tcorr using the same procedure as above and multiplied it by

our average Cv value to get ∆E for the system. We also had to calculate the ∆E of the

wire burned using the constants above (mass wire burned * ∆E{Comb, Fe} = − 5.86 kJ/g)
and subtracted this from the mass ∆E total to get the ∆Ebiphenyl. From this value we

calculated the ∆rxnH using equation 7:

For temperature we used the ambient temperature given by the calorimeter

reading device and for ∆ngas we found the change in moles of the system for each trial by

finding that there is a ∆n of 2.5 moles per mole of biphenyl and multiplied this number by

the number of moles of biphenyl in each trial. Using this formula we calculated the

average ∆rxnH to be -23.8740 + 0.0887 kJ. We then calculated this value in kJ/mol by

multiplying this value by the average number of moles per trial (0.003812.) to obtain a

value of -6262 + 23 kJ/mol. For all calculations we didn’t convert kJ to kJ/mol until the

very end since the Cv value has units of kJ/C and not kJ/mol*C.

Conclusion:

The data taken from NIST Webbook says that the enthalpy of combustion for

biphenyl is -6250 + 20 kJ/mol at standard temperature and pressure. Our average value

was -23.8740 + 0.0887 kJ divided by the average number of moles per trial (0.003812

moles) = -6262 + 23 kJ/mol. Our experimental value is within the standard deviation of

the literature value and is therefore accurate and statistically significant. There were a few

sources for error in this experiment. The first potential source for error was in creating an

estimated trendline for the straight portions of the graph used to calculate the ∆Tcorr

values. The equation for the line was based entirely on what points we felt made the

straightest line and had a potential for error as some of these lines had R^2 values of
< .95. There is also a potential for error in the calculation for the weight of the residue of

the wire as in two trials we had a higher residue weight then that of the wire.

References:

“NIST Standard Reference Database 69.” NIST Chemistry Webbook. U.S.

Secretary of Commerce, June, 2005.

<webbook.nist.gov/cgi/cbook.cgi?Name=Biphenyl&Units=SI&cTG=on&cTC=on&cTP=

on&cTR=on>