Absorption Spectrum of Iodine Vapor

Brennett Rodseth May 2, 2013 Physical Chemistry 2 Lab

Brennett Rodseth 4/30/13 Absorption Spectrum of Iodine Vapor Abstract: In this lab, we determine the properties of the ground and first excited electronic states of the iodine molecule by determining the molecular potential parameters from the UVVisible absorption spectrum of iodine in the vapor phase to find the dissociation energies at each state and respective potential energy well depths. The spectrum peak values were analyzed using a Birge-Sponer extrapolation to see energy differences of absorption peaks and quantum vibrational states. The ground state of the vibration level was found to be 150 kJ/mole, which was relatively similar to the energy of the actual value of 151.234 kJ/mole. The calculations were only off by 1.2%. Introduction: The purpose of this experiment is to determine the properties of the ground and first excited electronic states of the iodine molecule by determining the molecular potential parameters from the UV-Visible absorption spectrum of iodine in the vapor phase to find the dissociation energies at each state and respective potential energy well depths. The violet vapor visible light of iodine at higher temperatures is from the gaseous iodine molecule absorbing electromagnetic radiation that lies in the visible region of the spectrum. In this, the UV-visible absorption spectrum of iodine for the most part lies in the range 450 nm to 650 nm or 22,222 cm-1 to 15,385 cm-1. The translations that give rise to the absorption spectrum take place between the ground state of the iodine molecule and the excited electronic state, and nearly all are in the ground vibrational state (=0). The potential energy experienced by the electrons in a given state is described by a potential energy curve, and the energetics of the entire system is commonly depicted using a potential energy diagram. A Morse potential energy diagram showing the first three electronic states of molecular iodine is shown in Figure 1.

Figure 1: A Morse potential energy diagram for Iodine. The curve X describes the ground electronic state, and the curves A and B describe excited electronic states. The horizontal lines within the curves indicate the vibrational energy levels within the particular electronic state.

In figure 1, you can see some of the transitions that give rise to the absorption spectrum of molecular iodine. Not all translations are observed because electronic transitions take place much more quickly than the molecular vibration. A few values we will look at are the , which is the difference in lengths of adjacent peaks, De and De, which are the well depths of a Morse potential graph of each state, and Do and Do which are the dissociation energies of each state. To calculate the energies, we will plot the two adjacent transition and +1, which will give us our Birge-Sponer Plot. This is an accurate approximation for the low intensities of the states. Plotting our values and fitting it to a liner model we will obtain an equation similar to Equation 1. ( )

For the line that was plotted we obtain , this will be the y-intercept and the term will be the slope of the line. The second anharmonicity term was neglected due to it does not have much affect on the system and easier calculations. Next we will use the area under this line or integrate the equation, which is equal to the dissociation energy of the lower state, Do. Knowing this we can then find the well depth of the lower state De giving us the energy required to dissociate at the lower state as shown by Equation 2.

To then find the dissociation energy of the second state we will take a slightly different approach. First, we must find the convergence energy, E* as shown on Equation 3.

Here the b is the vibrational frequency where the Birge-Sponer line begins and A is the area under the line from b to the point where the line crosses the x-axis. Knowing this we can then find the dissociation energy of the second energy, Do, by using Equation 4. ( ) The E(I*) is a value given in which is told to be 7603.15 cm-1 (Sime). Now having the dissociation energy, the final step is to find the total energy in the well depth in the second state. The well depth energy is found by using Equation 5.

In this equation, e is calculated by using Equation 6. Where e is given to be 215 cm-1 and e is the value obtained from the Birge-Sponer plot. Now we finally have everything we need to find the well depth energy for both states.

Experimental: In this lab, located at the University of Idaho Renfrew hall, we carried out our experiment. The spectra will be taken on a UV-Visible spectrophotometer. The iodine sample will be contained in a temperature controlled special quartz spectroscopy cell. First turn on spectra suite and allow the UV-Visible spectrophotometer to warm up. As you prepare the computer clean the spectrophotometer cell.

Example of UV-Visible spectrophotometer cell.

Once the UV-Visible spectrophotometer is warm and the program is running, select the absorption scale. Use the clean blank cell as the light background to filter out the noise of the cell from the program to isolate the iodine absorption in the program. For the dark background close the aperture of the UV-Visible spectrophotometer and select the dark background to record the noise. Take the spectrophotometer cell and place the solid iodine inside the cell and seal the cell. Iodine needs to be in a gaseous state to record absorbance. Use an industrial heat gun to heat up the cell and iodine to produce the iodine

vapor. The iodine sublimes and the cell now contains a sufficient amount of faintly purple iodine vapor. You will see the absorption spectra increase on the graph. Export the data to excel or take a screen shot. Make sure you shut down the apparatus and unplug the heat gun when you are finished.
Results:

Figure 3:

Figure 3: Graph of raw data from spectra-suite, absorbance versus wavelength for iodine gas.

Figure 4:

Birge-Sponer Plot
120 100 Change in Transitions 80 60 40 20 0 10 15 20 25 30 v'+1 35 40 45 50 y = -1.6963x + 119.69 R = 0.7863 Birge-Spooner Linear (BirgeSpooner)

Figure 4: Birge-Sponer plot, change of transition versus v+1 fit to a liner fit.

Table 1: First State Do(cm^-1) 4222.6 e(cm^-1) 119.69 De(cm^-1) 4282.5 De(kJ/mol) 51.2

Table 1:Results of calculations for the ground state

Table 2: Second State b(cm^1) 19496.5

A'(cm ^-1) 598.3

E*(c m-1) 20094

E(I*)(c m^-1) 7603.15

Do"(cm e(cm ^-1) ^-1) 12491. 215

e"(cm ^-1) 95.31

De"(cm De"(kJ/m ^-1) ol) 12539. 150

97

.9

75

Table 2: Results of calculations for the excited state

Discussion: To first begin the calculations in the experiment, the raw data graph of absorbance versus wavelength (Figure 2), calculate the peak heights of the oscillating line. This process was explained and made simple by a designed step-by-step process (Sime). These peaks correspond to the different transitions taking place from the lower state to the higher state. The heating of the iodine with the industrial heating gun caused the highly populated ground state to shift its numbers to the higher vibration states. We actually watched the graph in figure 2 shifts as we heated the photocell. After all the peaks had its wavelengths converted to wavenumbers, we took the difference between peaks using our fitted line. We were then able to obtain our Birge-Sponer plot to give us the necessary values expressed in Table 1 with the equations from the introduction. We always found the energy from the lowest vibration state up the max quantum energy, since energy is quantized. This then would allow us to find the energy from the bottom of the well up to the point of the bond breaking to get a better approximation for the amount of energy needed. This is expressed and shown in better detail as seen in Figure 1. We did not consider the contribution from the rotational energies because the transitions of rotational energies are contained within the vibrational levels. From the quantum mechanics selection rules we know that the transitions of rotational energy can only go up or down by one energy level. The heating of the iodine in the photocell caused the higher vibrational states to be much more populated and transitions in the rotational energy were negligible. Doing our calculations we obtained our value for the ground state to be 150 kJ/mole, which was relatively similar to the energy of the actual value of 151.234 kJ/mole. The calculations were only off by 1.2%. This goes to show that the assumptions made and the difficulty in designating the peaks was done quite successfully.

Conclusion: In this experiment using the UV-Visible spectrophotometer as a method of finding the dissociation energy of an iodine molecule is a very successful and accurate approach. This is true for our experimental values because they are compared those of the actual tabulated values. This allowed out experiment to have low error and replicable data if further exploration is needed. The Birge-Sponer Plot turned out to be successful and beneficial extrapolation in finding the dissociation energy of the iodine molecule.

Refrences: Levine, Ira N. Physical Chemistry. Boston: McGraw-Hill, 2002. Print. Garland, Carl W., Joseph W. Nibler, and David P. Shoemaker. Experiments in Physical Chemistry. Boston: McGraw-Hill Higher Education, 2009. 437. Print. United States. Department of Commerce. NATIONAL BUREAU OF STANDARDS.NATIONAL BUREAU OF STANDARDS. By Darwent. N.p., n.d. Web. 31 Mar. 2013. <http://www.nist.gov/data/nsrds/NSRDS-NBS31.pdf>. Sime, Rodney J. Physical Chemistry: Methods, Techniques, and Experiments. Philadelphia: Saunders College Pub., 1990. 663. Print. Garland, C. (2003). Experiments in physical chemistry . (pp. 423-432). New York: McGraw Hill.