Loyola College M.Sc. Chemistry Nov 2006 Molecular Spectroscopy Question Paper PDF Download

                          LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034

M.Sc. DEGREE EXAMINATION – CHEMISTRY

AD 24

THIRD SEMESTER – NOV 2006

CH 3810 – MOLECULAR SPECTROSCOPY

 

 

Date & Time : 30-10-2006/9.00-12.00      Dept. No.                                                   Max. : 100 Marks

 

 

PART A

Answer ALL the questions.                                                 (10 x 2 = 20 Marks)

  1. Convert 0.15 nm to Hz and state what sort of transition this corresponds to.
  2. What are stokes and anti-stokes lines?
  3. Name two techniques to enhance the sensitivity of the spectral lines.
  4. What is the basic principle of Mossbauer spectroscopy?
  5. From the relative abundance of the (M+2)+ peaks in the mass spectra, can you distinguish chloro compounds from Bromo compounds?
  6. State the principle of PES. What is the essential difference between XPES and UV-PES?
  7. A free electron is placed in a magnetic field of strength 1.3 T. If ge is 2.0023 and βe is 9.274 x 10-24 JT-1. Find the ESR frequency in GHz.
  8. What are the advantages of using TMS as the standard in NMR experiments?
  9. Compare the 1H and 13C NMR spectra in terms of the range of chemical shifts and intensity of the peaks (peak areas)
  10. What is spin-spin relaxation?

PART – B

Answer ANY EIGHT questions                                          (8 x 5 = 40 Marks)

  1. What are the factors that affect the width of the spectral lines? Explain any two of them.
  2. The observed infrared absorption and Raman spectral lines of Chlorate ion (ClO3) are given below. Predict the structure of Chlorate ion.
Raman Frequencies (cm-1 )                        IR Frequencies (cm-1

450 (depolarized)                                           434 (^)

610 (polarized)                                               624 (||)

940  (depolarized)                                          950 (^)

982 (polarized)                                               994 (||)

 

  1. The frequencies of vibration of the following molecules in their v = 0 states are HCl: 2885 cm-1; D2: 2990 cm-1; DCl: 1990 cm-1 and HD: 3627 cm-1, calculate the energy change in the reaction HCl + D2 à DCl + HD.
  2. The mass spectrum of a compound having the empirical formula C11H12O2, shows the following peaks at m/e : 78,105 (Base peak), 122, 135,176 (Molecular Peak). Identify the compound and account for the fragments.
  3. At what temperature will the number of I2 molecules in the v=1 level be one-tenth of that in the v=0 level? Given = 214.6 cm-1;xe = 0.6 cm-1 and k = 1.38 x 10-23J K-1.
  4. Explain Quadrupole mass spectrometer.
  5. Explain what is Zero Field or Crystal Field Effect in the fine structure of ESR

and the factors that contribute to that.

  1. State and explain Franck-Condon Principle. With diagrams explain the

variations in intensity of electronic spectra explained by this principle?

  1. What is population inversion? Prove that a population inversion cannot

be achieved in a two level system while it is possible in a three level system.

  1. (a) With an example explain Diamagnetic Anisotropy.

(b) The chemical shift of the CH3 protons in diethyl ether is ∂ = 1.16 ppm and that of the CH2 protons is 3.36 ppm. What is the difference in local magnetic fields between the two regions of the molecule when the applied field is 16.5 T?

  1. Predict

(a) the spin-spin splitting pattern for the protons of neopentane molecule

and the peaks’ intensity distribution.

(b) the hyperfine splitting of the ESR spectrum of ۰CD3 and ۰CHD2 radicals.

[note: the spin of D is 1]

  1. Explain the principle of 2D NMR highlighting its advantages.

PART – C

Answer ANY FOUR questions                                            (4 x 10 = 40 Marks)

  1. a) Three consecutive lines in the rotational spectrum of a diatomic molecule are observed at 84.544, 101.355 and 118.112 cm-1.  Assign these lines to their appropriate J’’ àJtransitions and deduce the values of B and D.
  2. b) How are meta stable ions produced and how are they useful in identifying the molecular formula of a compound?
  3. a) The fundamental band of HCl is centered at 2886 cm-1.  Assuming that the internuclear distance is 12.76 nm, calculate the wave number of the first two lines of each of the P and R branches of HCl.
  4. b) Explain the pure rotational spectra of symmetric top molecules.
  5. a) Explain the fact that the Mossbauer spectrum of [Fe(CN)5NO]2- gives two lines whereas [Fe(CN)6]4- spectrum gives one line.
  6. b) In the rotational Raman spectrum of HCl, the displacements from the exciting lines are represented by Dn = ± (62.4 + 41.6 J) cm-1.  Calculate the moment of inertia of the HCl molecule.
  7. Explain the following with a suitable example:

(a) spin-spin coupling in 1H-NMR

(b) mechanism of spin-spin coupling for geminal protons

(c) the multiplicity and intensity distribution represented by the ‘coupling tree’

 

  1. (a) Explain briefly: (a) spin-spin relaxation (b) Fourier Transformation Technique.

(b) Sketch the esr spectrum of °CH3 and explain its nuclear hyperfine splitting.

 

  1. (a) What are asymmetry electric field gradient and asymmetry parameter, η? How

are they related? What is the significance of η?

(b) Taking any laser as example explain the three most important components

of a laser?

 

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