Resonance Energy of Naphthalene by Bomb Calorimetry

Monica Patel, Christy Crowly, Casey Theys and Kyle Crane Department of Chemistry, The Pennsylvania State University, University Park, PA16802 Submitted: November 1stth, 2010 (CHEM 457, Section 2)

This experiment was used to determine the heat of combustion of naphthalene and to compare that value to the literature value. The experimental value of Hcomb, naph s was determined to be -5212 KJ/mol. Comparing it to the literature value of -5160 KJ/mol gives a 1% error. This error was determined to be the cause of resonance stabilization. An experimental value of Hcomb, naph s was calculated by using Hess¶s Law, and was determined to be -5320 KJ/mol.

Introduction

Bomb calorimetry is often used to determine the standard enthalpy of combustion of a substance (hydrocarbons). The standard enthalpy of combustion can then be used for determining other thermochemical properties such as heats of formation, bond energies and resonance stabilization energies of aromatic compounds. Naphthalene, for example, is one such compound. A bomb calorimeter is a sealed container, where a weighed sample of substance is placed in contact with an ignition wire inside. The bomb is filled to a pressure with O2, and then sealed. The bomb is then placed in a known amount of water. An electric current is passed through a wire to set fire to the mixture. As the combustion takes place, the heat created raises the temperature of the calorimeter and its surrounding water. This temperature change is measured with a thermometer. The data collected is then used to calculate the enthalpy of combustion of a substance. The combustion of naphthalene is an exothermic process, and can be represented in the following equation.

C10H8 (s) + 12O2 (g) ---> 10CO2 (g) + 4H2O (l)

Hcomb, naph s = -5160 KJ/mol (1)

The energy released from this reaction is accounted for in the breaking and forming of bonds. The complete combustion of hydrocarbons usually produces two products: carbon dioxide and water. If nitrogen, however, were present within the reaction, nitric acid would be produced in the calorimeter.

The following equations are used to calculate the theoretical enthalpy of combustion of naphthalene:

C10H8 (g) + 12O2 (g) ---> 10CO2 (g) + 4H2O (g) C10H8 (s) --> C10H8 (s) H2O (l) --> H2O (l) C10H8 (s) + 12O2 (g) ---> 10CO2 (g) + 4H2O (l)

(2) (3) (4) (5)

To determine the unknown enthalpy of combustion of a substance, a sample with a known enthalpy of combustion is first tested using the bomb calorimeter. By using the following equation, the specific heat of the calorimeter may be calculated.

Ccalorimeter = (-) [ Usamplemsample) + ( Ufuse mfuse)] / T

(6)

Where Usample is the heat of combustion of the sample or fuse in J/g, msample is the mass of the sample combusted, mfuse is the difference between the initial mass of the fuse and the mass of the fuse after combustion, and T is the difference between the final and initial temperatures of the water.

The temperature change of the experiment will be recorded and then the temperature at 60% completion (T60%) will be determined. Ti is the temperature corresponding to the final point of the ignition line and Tf corresponds to the temperature corresponding to the first point of the post-ignition line. The internal energy of Naphthalene can then be calculated by using the following equation:

U = Ccalorimeter (Tf - Ti)

(7)

The actual enthalpy change, taking into account the change in moles, can finally be determined by the equation

H = U + nRT

(8)

where

n is the change in moles of gas within the reaction, R is the universal gas constant, and

the T used is T60%. Hess¶s Law can determine thermochemical information of reactions by using the summation of the individual bonds or estimating from the manipulation of bond energies. Resonance stabilization energy is associated with delocalized electrons from Pi bonds and can then be determined by calculating the difference between the experimental value for the heat of combustion and the theoretical value.

Experimental

The procedure for this experiment is detailed in the Lab Packet, but will be written in brief here. A benzoic acid pellet that was 1.02 g was placed in the combustion pan of the calorimeter by using tweezers. A 10 cm piece of nickel alloy fuse wire (Paee 45C10) was massed and then strung through and wrapped tightly around both ends of the electrode. The middle fuse draped closely over the benzoic acid pellet in the middle of the pan. Using a pipette and a 10 mL graduated cylinder, 1.0 mL of distilled water was placed in the bottom of the bomb, below the pan. The bomb was then closed by screwing on the lid securely by hand. The bomb was then charged with oxygen by filling it to 15 atm, and then venting it to about 1 atm and then repeating that procedure once more before finally filling it to 30 atm. The bomb was then set into the bucket and assured that it was not touching the walls of the calorimeter. The electrical connections were plugged into the top of the bottom, and the bucket was then filled with 2.0 L of deionized water at room temperature. The lid of the calorimeter was placed with the stirrer in the back and the thermometer in the front. The lid used in this experiment was taken from a different calorimeter (blue as opposed to red) because it was in better working order. The program on the computer was allowed to run for 5 minutes to create a steady temperature called the pre-ignition line, and then the bomb was ignited until it reached a maximum base line called the post ignition line. After about 5 minutes more, the program was stopped and the data was saved into an excel file. The entire system was disassembled and then reassembled but this time using a .561 g pellet of Naphthalene.

Results and Discussion In order to find and analyze the thermochemical properties given by the combustion of benzoic acid and naphthalene, the following two graphs were created (Figure 1 and Figure 2).

T60%

Figure 1: Combustion of Benzoic Acid

Figure 2: Combustion of Naphthalene

The following data listed in Table 1 had to be used in order to determine the thermochemical properties of the samples.

Compound Benzene Naphthalene

m sample (g) 1.02 0.5606

m fuse (g) Ti (°C) Tf (°C) DT (°C) 0.0091 25.8 27.8 2 0.0073 25.8 27.6 1.8 Table 1: Collected data from experiment

T 60% (°C) 27.1 26.9

The heat capacity of the calorimeter was determined to be -13.7 KJ/goC (Equation 2), and the heat of combustion of naphthalene, U, was found to be 5217 KJ/mol (Equation 3).

Next, the experimental enthalpy of combustion of naphthalene, Hcomb, naph s was calculated to be -5212 KJ/mol. The literature value of the enthalpy of combustion for naphthalene is -5160 ± 20 KJ/mol. The literature value of the heat of combustion of Naphthalene is lower than the experimental value found. This is due to the unaccounted for resonance energy in the Hess¶s Law calculation. Resonance energy gives stability, which causes a decrease in energy required to break the bonds in the molecule. Therefore, the literature value is reported as being lower than the calculated experimental value. The theoretical Hcomb, naph s was calculated by using equations 2, 3, 4 and 5, and was determined to be -5320 KJ/mol. The method of using these equations is called Hess¶s Law. Hess¶s law does not take into account stabilization energy, so it can be used to determine the resonance stabilization energy by subtracting its value from the experimental heat of combustion. The resonance energy of naphthalene was determined to be 108 KJ/mol. Hess¶s law is more inaccurate because it does not take into account resonance stabilization energy which can result in large errors.

The absolute value difference of the literature value and the experimental value of enthalpy of combustion is 161 KJ/mol. The experimentally determined Hcomb, naph s and the

literature value are similar, and show a 1% error. This makes the experiment successful.

Conclusion The literature value of the enthalpy of combustion of naphthalene, the theoretical and the experimental all differ. The literature value takes into account resonance energy, which would lower the heat it takes to break bonds, causing this value to be lower than the experimental value found. The resonance energy of this experiment was determined to be 108 KJ/mol. Overall, the experiment was a success.

Acknowledgement I would like to acknowledge the group members previously mentioned, along with our teaching assistant Nicole Thom and our professor, Dr. B. H. Milosavljevic, for all their assistance throughout the work of this lab.

Resources

(1). Milosavljevic, B.H Lab Packet for CHEM 457: Experimental Physical Chemistry, Resonance Energy of Naphthalene by Bomb Calorimetry. University Press: University Park, 2009 (2). "Bomb Calorimetry." Chemweb. Web. 31 Oct. 2010. <http://www.google.com/#sclient=psy&hl=en&q=bomb+calorimetry&aq=f&aqi=g4go1&aql=&oq=&gs_rfai=&pbx=1&fp=b2da8a77dcd93603>.

(3). "Bomb Calorimetry." Hope College Chemistry Department. Hope College. Web. 02 Nov. 2010. <http://www.chem.hope.edu/~polik/Chem345-2000/bombcalorimetry.htm>.