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Abstract

The high-resolution UV-Vis spectrophotometer was used to obtain the spectra of iodine in its excited state along with bromine water. Spectrum peak values were analyzed using a BirgeSponer extrapolation to see energy differences of absorption peaks and quantum vibrational states. The iodine experiment produced data concluding in results very close to literature values. The ground state bond dissociation energy was found to be 155.88 kJ/mol and the excited state dissociation energy was found to be 57.4944 kJ/mol.

Introduction

In this experiment the visible absorption spectrum of iodine was used to find the dissociation energy among other useful values that can be determined with this spectrum, such as: 1. Difference in the wavelength of adjacent peaks in the absorption spectra. 2. Potential well depths of each state.

Electrons make transitions from a lower state [indicated with a double prime ()] to a higher state (), when excited by the UV-Vis absorption Spectrophotometer. These transitions, which are vibrational, are observable because iodine vapor absorbs electromagnetic radiation in the visible light region. (2) This is why we can see the purple color of vaporous iodine fumes.

P-Chem II lab Tianna Drew

The potential energy diagram labeling all values determined by this transition is shown here. (3)

Figure 1. A Morse potential energy diagram (Figure 1) can be used to describe the behavior of a molecule as that molecule becomes excited. The vibration movements can be demonstrated with a harmonic oscillator model, but this does not account for the fact that the molecule can break apart when excited, and jump to a higher state. Internal energy and translational energy are combined to form the total energy of a diatomic molecule. Because there is no translational energy of a diatomic molecule, only the internal energy will be considered from here on. This energy is comprised of the electronic, vibrational, and rotational energies, as shown: (1) To calculate the dissociation energy of iodine, approximations must be made because one cannot access the states near the dissociation energy. This is due to the states low intensities.

P-Chem II lab Tianna Drew

One approximation/ technique is to use the Birge-Sponer treatment. Two adjacent transitions, and +1, are plotted against each other to make a Birge-Sponer plot. The plot is a straight line with the function: (1) . (2)

The second order anharmonicity constant ( ) was neglected, and the y-intercept is . The slope is [ ], where is the first order anharmonicity constant. Next, the area under the plot is used to determine the dissociation energy ( of the lower state. and are found using and . These constants are portrayed in figure 1. To find the upper state dissociation energy ( ) the following equation is used: (3) In this equation, E(I*) is a constant (given to be 7603.15cm-1 ) and E* is the convergence limit, given by the equation: (4) where is the frequency of where the extrapolation of the Birge-Sponer plot first begins and is the area under the curve from to the x-intercept. Then can be calculated using this equation: (5) where is a constant (given at 215cm-1). Now the oscillator strength of I2 can be found: (6) where is the reduced mass of the molecule, is the speed of light, and defined above. = which is

The Morse parameter, which enables us to graph the Morse potential curve, is defined as:

P-Chem II lab Tianna Drew

Experimental

A high-resolution UV-Vis spectrophotometer with a resolution of 0.2nm or better is required in order to draw out the detailed spectrum necessary to analyze vibrational processes in this experiment. (1) A sample of solid iodine is placed in a sealed 100mm sample cell, in which its fumes can be scanned by the spectrometer at room temperature, or at higher temperatures using a heat gun. The higher temperature makes the iodine vapor much easier to get an impressive spectrum from. Bromine water (3%) was also used in the spectrometer in order to contrast the practicality of running the electronic spectrum of a condensed phase.

Results

Plot of the electronic absorption spectrum of I2 vapor (raw data)

Figure 2.

P-Chem II lab Tianna Drew

Figure 3 Graphing the spacing between the vibrational energy levels of the I2 vapor spectrum against the quantum vibrational numbers v of the excited electronic state produces a Birge-Sponer plot.

Figure 4. The linear regression of the Birge-Sponer plot gives the vibrational constants for the excited state energy expression and the total number of vibrational states. = 6.1001x10-3 max = 84

P-Chem II lab Tianna Drew

The bond dissociation energy of the excited state was found using the spectral data in conjunction with the Birge-Sponer plot. Then the dissociation energy of the ground state could be calculated using D0, data from the spectrum, and the known atomization energy of iodine. = 4806.20 cm-1 or 57.494 kJ/mol = 13027 cm-1 or 155.88 kJ/mol

Discussion

After assigning the quantum number v=25 to the absorption line at 18312.50 cm-1 in Figure 2, the rest of the quantum numbers were assigned accordingly.(4) Because the iodine was heated in the experiment, the population of I2 molecules shifted. It went from being mostly populated in the ground state to a large increase in the population in a vibronic state, which made it difficult to assign specific wavenumbers to each vibrational state. () This increase in population of molecules in the v=1 and v=2 states intensifies the spectral lines created by the transitions.(5) These hot bands increase the complicatedness of the iodine absorption spectrum (Figure 2). The interference of the hot bands was intense enough to skew the exact locations of the v=0 to v= n transition band heads. To make things easier, the transition locations within each peak region were labeled consistently, the ratio of the location of the absorption line at 18312.50 cm-1 to the width of its peak was calculated, then superimposed on the other peaks to give specific wavenumber values for each v=0 to v= n transition.

To prove a point, it was instructed that the spectra of bromine water be taken. The results were a whole lot of nothing. UV-Vis spectroscopy does not pick up the peaks for Br2 water because liquids and solids do not give vibrational information. This is because the condensed phases collide with each other often enough to give their peaks lifetime broadening. Lifetime broadening is when collisions between particles shorten the life of their quantum states. According to the uncertainty relation , as the lifespan of a state decreases, its energy uncertainty increases which means broad absorption peaks are observed.(6) A large, single peak represents all transitions in the case of liquid bromine (Figure 3). According to calculations, using in equation (2) shows 84 total vibrational states in the excited electronic state of I2. A literature value found at the University of Rhodesia calculated 86 quantum vibronic levels in the excited state of I2. Due to the noise in the absorption spectrum (Figure 2), direct measurements of the spacing of transitions could only be made with from v= 0 to v= 33, which represents only 2% of the

P-Chem II lab Tianna Drew

energy summed from v= 0 to v= 33. It can be inferred that (v) for values of v > 33 will be small enough to disregard, in comparison to the partial sum. This means the remaining energy changes to be totaled can be expressed as an integral from v=33 to vmax=84. The expression for the sum of energies that total the bond dissociation energy D0 of the excited state then becomes: dv (8) Evaluation of equation (8) gives D0 = 4806.20 cm-1 or 57.494 kj/mol. The literature figures for D0 and D0 are 4046 cm-1 and 152.532 kj/mol, respectively.(7,8) The value of Do differs by 16%, and the two figures for Do differ by 2.1%.

Conclusion

The values of bond strength of the diatomic molecuse iodine (I2) calculated in this experiment ( 155.88 kJ/mol for the ground state and 57.4944 kJ/mol for the excited state) were in close agreement with published values. This is true for the number of vibrational states (84) in the exited electronic state as well. The main goal to find the dissociation energy of the I2 molecule was successful in that the data and results were again close to the literature results. Using a high-resolution UV-Vis spectrophotometer, it is a fairly simple method to obtain a spectrum which can be interpret and manipulated to find many values relative to ones field of research. The UV-Vis spectrophotometer was used because Iodine vapor absorbs radiation at wavelengths corresponding to yellow light.()

References

1. Brittain, E. F. (1970). Introduction to molecular spectroscopy. (pp. 80-83). New York: Academic Press Inc. 2. Garland, C. (2003). Experiments in physical chemistry. (pp. 423-432). New York: McGraw Hill. 3. Google Images 4. Steinfeld, J. (1965). Spectroscopic constants and vibrational assignment for iodine. The Journal Of Chemical Physics, 42(1), 25-33. 5. Chapman, D. (2012, March 22). The electronic spectrum of iodine. Retrieved from http://home.sou.edu/~chapman/ch445/Iodine.htm 6. Hiereth, M. (2005, January 20). Lifetime broadening. Retrieved from http://www.pci.tubs.de/aggericke/PC4e_osv/Spectroscopy050119/node7.html

P-Chem II lab Tianna Drew

7. McNaught, I. (1980). The electronic spectrum of iodine revisited. Journal of Chemical Education, 57(2), 101-105. 8. Barrans, R. (2002, December 10). Fluorine, iodine, and bond energy. Retrieved from http://www.newton.dep.anl.gov/askasci/chem00/chem00945.htm

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