282

University Practical Physics

Theory: At ordinary temperatures almost all the molecules are in the ground state. 'Whenwhite light is passed through iodine vapour, those particular radiation for which hu is equal to the energy gap between the ground state to any of the electronically excited states have a chance of being absorbed by the iodine vapour. Hence series of dark lines corresponding to the frequencies for which absorption occures are seen in a background of the continuous spectrum of white light. The angular positions of different absorption bands can be measured with a spectrometer and grating, using the relation, (e+d) sin e = nA .... (i) Method: Mount an incandescent lamp in a housing with an opening along the axis of the collimator of a spectrometer. Adjust the spectrometer as described in chapter 12. Set the grating for the normal incidence as described in chapter 14. A well defined continuous spectrum is obtained in the field of view of the telescope of the spectrometer. Now introduce a glass tube T containing some iodine grains in it between the lamp and the collimator, as shown in Fig. 17.1. Few dark bands are observed. Measure these dark bands as done in other grating experiments.

Fig; 17.1. Experimental

set-up,

Repeat the experiment with tubes of various lengths. One can find the effect of warming the iodine grains. Analysis and Criticism : The separation of the successive bands is found to be so small that the positions of these bands can not be measured accurately. Therefore the measurements are made from the farthest available band on the longer wavelength side. The positions of every fifth band are recorded and the bands are assigned numbers as no' no+5, no + 10, - - - etc. From the direct image readings and the angular positions of different absorption bands, the angle e and hence the A values are evaluated. Using the relation E = hu = he/A, the energy level diagram is e~tablished. The 1 m length of the tube is required to provide satisfactory amount of absorption at room temperature. A short tube about 20 cm long is sufficient ifit is warmed up by some arrangements, say a spirit lamp. It is seen that the warming up of the

Atomic Spectra

283

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tube makes the absorption bands quite strong till almost the whole spectrum on the violet side disappears. It is due to the fact that with the rise of the temperature the vapour density increases .md the more molecules enter in the path and hence more absorption takes place. The excitation energy for the iodine molecule can be measured from the lowest value of frequency u. The energy corresponding to the farthest available band on the longer wavelength side need not really belong to the transition to the ground state. Hence the observed value hu may not give the true value of excitation energy. EXPERIMENT

"

NO. 17.3

Object: To determine theforce constant and Vibrational constant for the iodine molecule from its absorption fJpectrum. Apparatus: Same as in Exp. No. 17.2.
Theory : The force constant k for the excited electronic state of the iodine molecule can be obtained from the values for the successive vibrational levels. The frequency difference ~u of two successive vibrational levels is related with k as,

~u = c = c ~ ~ = 2rc~; or 1 (k
where
Jl

k = 4rc"C"(~ ;:;)" Jl.

= reduced mass of iodine molecule.

The separation ~ ;:; for one band is called the vibrational constant.

Method: As described earlier in experiment No. 17.2. Discussion: From the observed values of e, the wavelengths and hence
the wave numbers ;:; are obtained for the no' n" + 5,
11"

+ 10, levels. The

separations ~ ;:; are found to be nearly constant in the beginning, thereafter steadily fall is observed. A graph between ;:; and n is plotted. From this

graph ~ ;:; for one band is calculated. This is the measure of the vibrational constant for the iodine molecule in the concerned excited state. The reduced mass of the iodine molecule = mass of iodine atom/2
:. Jl = Y2 x 127 atomic mass units = 10-27 kg. Thus the force constant k for the iodine molecule is calculated, the value so obtained is for the excited electronic state of iodine, not for the

ground state.