(DCHE 01) M.Sc. (Previous) DEGREE EXAMINATION, DECEMBER First Year. Chemistry. Paper I GENERAL CHEMISTRY. PART A (4 10 = 40 marks)

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1 (DCHE 01) M.Sc. (Previous) DEGREE EXAMINATION, DECEMBER First Year Chemistry Paper I GENERAL CHEMISTRY Time : Three hours Maximum : 100 marks PART A (4 10 = 40 marks) Answer any FOUR questions. 1. Write notes on the spectra of rigid rotor. 2. Explain the basic principles of NMR spectroscopy. 3. What is the effect of isotopic substitution in the study of rotational spectroscopy? 4. Discuss the vibrational spectra of a harmonic oscillator. 5. Write notes on regression analysis and Gaussian distribution.

2 6. What are absolute and relative errors? How are they propagated? 7. What is the difference between an arithmetic statement and arithmetic expression? Explain how integer mode, real mode and mixed mode expressions are evaluated. 8. Write a Fortran program for summing a power series. PART B (4 15 = 60 marks) Answer ALL questions. 9. (a) Write notes on spectra of rigid rotor and nonrigid rotor. (b) Explain the basic principles of ESR spectroscopy and discuss the significance of hyperfine coupling. 10. (a) Discuss the vibrational-rotational spectra of a diatomic molecule. (b) Explain the electronic spectra of diatomic molecules. 2 (DCHE 01)

3 11. (a) Explain the terms precision and accuracy. Describe the various factors that quantify precision and accuracy. (b) Write notes on students t-test and F-test. 12. (a) Write a flow chart and Fortran program for calculation of rate constant of a first order reaction. (b) What are control statements? Explain the syntax and use of conditional/unconditional statements. 3 (DCHE 01)

4 (DCHE 02) M.Sc. (Previous) DEGREE EXAMINATION, DECEMBER First Year Chemistry Paper II INORGANIC CHEMISTRY Time : Three hours Maximum : 100 marks PART A (4 10 = 40 marks) Answer any FOUR questions. 1. Explain the Black body radiation and Planck s temperature radiation law with suitable examples. 2. Discuss the L-S and J-J coupling schemes. 3. Explain the concept of resonance MO treatment of H2 molecule. 4. Explain in detail about : (a) (b) Hydrogen bonding Fajan s ruler. 5. Discuss the need and importance of orpel diagrams.

5 6. What are the structural factors affecting stability? Explain. 7. Discuss the structure and bonding of silicones. 8. How do you classify the labile and inert complexes of valence bond and CFT? PART B (4 15 = 60 marks) Answer ALL questions. 9. (a) Describe the Schrodinger s wave equation for an electron in a box. (b) Explain the following : (i) (ii) de Broglie hypoflurin Larmor precessional motion of orbit. (iii) Compton effect. 10. (a) What is meant by VSE PR theory? How it useful in determination of bond order, bond length and bond angles with suitable examples. (b) Discuss the types of solids interms of covelent crystals, ionic solids, clathrates and clathrates. 2 (DCHE 02)

6 11. (a) State the John-Teller theorem. Discuss its application complexes with suitable examples. (b) (i) What is meant by Chelate effect? Discuss its role in stability of complexes. (ii) Describe ph method for determination of stability of constants of complexes. 12. (a) (i) Differentiate between complimentary and non complementary reaction with simple example. (ii) Discuss the basic ideas of inner and outer splene mechanism with examples. (b) (i) What is meant by trans effect? Explain its importance. (ii) Discuss the properties, structure and bonding of P-N cyclic compounds. 3 (DCHE 02)

7 (DCHE 03) M.Sc.(Previous) DEGREE EXAMINATION, DECEMBER First Year Chemistry Paper III ORGANIC CHEMISTRY Time : Three hours Maximum : 100 marks PART A (4 10 = 40 marks) Answer any FOUR questions. 1. (a) Discuss the rosance and cross conjugation with suitable example. (b) Discuss the asymmetric synthesis with suitable example. (10) 2. Explain the nucleophilic substitution at a uncyclic carbon. (10) 3. (a) What is meant by regio selectivity? Explain its importance. (b) Give the potential energy diagram of transistion status and intermediator. (10)

8 4. State and explain the Gatter mann-koch reaction. (10) 5. Give any two methods for the generation of carbonations and explain the characteristics of free radicals. (10) 6. Discuss the conformation of butane on the basis of energy consideration. (10) 7. Discuss the mechanism of the following : (a) Parkins reaction (b) Witting reaction. (10) 8. Explain the mechanism and circulation involved in pyrolytic elimination reaction. (10) PART B (4 15 = 60 marks) UNIT I 9. (a) (i) What is meant by anomaticity? How Huckel s rule explain it. (ii) Discuss anomaticity of benzonoids and non benzonids compounds. 2 (DCHE 03)

9 (b) (i) Explain the elements of symmetry with suitable examples. (ii) Discuss the effect of conformation on reactivity in cyclohexane derivatives. UNIT II 10. (a) What are free radicals? Give any three methods for the generation of carbenes Explain the structure, stability and reactivity of nitrenes. (15) (b) Discuss the following terms with suitable examples (i) Mixed SN reaction (ii) Neighbouring group participation (iii) Region selectivity. (15) UNIT III 11. (a) Write a short note on the following terms (i) IPSO attack (ii) Hydroboration (iii) NBS. (15) 3 (DCHE 03)

10 (b) Give an account of the following reactions (i) Sand mayer reaction (ii) Hens dicker reaction (iii) Mechanism of addition reaction. UNIT IV 12. (a) Explain the differentiation among the E 1, E 1 CB and E 2 reactions with suitable examples. (b) Discuss the mechanism of metal hydride reduction of saturated and unsaturated acids and ester with suitable examples. 4 (DCHE 03)

11 (DCHE 04) M.Sc. (Previous) DEGREE EXAMINATION, DECEMBER First Year Chemistry Paper IV PHYSICAL CHEMISTRY Time : Three hours Maximum : 100 marks PART A (4 10 = 40 marks) Answer any FOUR questions. 1. Explain the terms free energy, entropy and enthalpy. How they are related? 2. Derive Gibb s Duhem equation. 3. Describe different types of radioactive equilibria with suitable examples. 4. Write a detailed note on semiconductors and insulators. 5. What are electro chemical cells? Explain briefly. 6. State and explain BET equation. Draw and explain Langmuir adsorption isotherm curve.

12 7. Write about absolute theory of reaction rate giving suitable examples. 8. State and explain laws of photochemistry. Add a note on Fluorescence emission. PART B (4 15 = 60 marks) Answer ALL questions. 9. (a) Derive classius clapeyron equation. (b) Write about Maxwell s partial relationships. (c) Derive thermodynamic phase rule and Raoult s law. (d) Write a note on partial molar quantities. 10. (a) Describe the principle of Isotope dilution analysis and radiocarbon dating. (b) Write the applications of radio isotopes in medicine and agriculture. (c) Define the terms Unit Cell and lattice energy. Write about Scottky and Frenkel defects. (d) Write a detailed note on scintillation counters. 2 (DCHE 04)

13 11. (a) Derive an equation for EMF of a cell with transference. (b) Explain the terms specific and equivalent conductance. How they vary with concentration? (c) (d) What is activity coefficient and explain how it is determined using EMF data. Write a note on reverse micelles. 12. (a) State and explain the collision theory of reaction rates. (b) Explain the mechanism of acid-base catalysis. (c) Write about photochemical equilibrium. Explain by giving suitable examples. (d) Explain the effect of temperature on reaction rates with suitable examples. 3 (DCHE 04)

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