M.Sc. (Previous) Chemistry DEGREE EXAMINATION, MAY 2007 Paper I - GENERAL CHEMISTRY. PART A - (4 x 10 = 40 marks) Answer any FOUR questions
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1 Time : Three hours M.Sc. (Previous) Chemistry DEGREE EXAMINATION, MAY 2007 Paper I - GENERAL CHEMISTRY (DCHE 01) 1. Discuss the types of molecular spectroscopic techniques and the sources of radiations used in them 2. Mention the basic principles of NMR and ESR techniques. 3. Write a note on electronic spectra of diatomic molecules. 4. Illustrate vibrational spectra of an harmonic oscillator. 5. Discuss the theory and techniques of sampling. 6. What is Gaussian distribution? Discuss its applications. 7. Write a note on Computer Hardware. 8. Discuss the statements relevant to input and output of a computer program written in MS- FORTRAN. PART B (4 x 15 = 60 marks) Answer ALL questions. 9. (a) Discuss the rotational spectra of diatomic molecules using rigid rotor model. What are the selection rules for microwave spectroscopy? (c) What is the isotopic effect on rotational spectra? 10 (a) Describe the principle, selection rules and applications of vibrational spectroscopy. Discuss the principle and applications of UV-visible spectroscopy. 11. (a) What are the various types of errors found sampling and data analysis and how are they minimized? Write an essay on regression analysis. 12. (a) Write a computer program in MS-FORTRAN for solving vander Waals equation. Write a flow chart and computer program in MS-FORTRAN for the application of Beer s law by least sqare method.
2 Time : Three hours M.Sc. (Previous) Chemistry DEGREE EXAMINATION, MAY 2007 Paper II - INORGANIC CHEMISTRY 1. Write a note on atomic spectra of alkalimetals. 2. Describe black body radiation and Planck s temperature radiation law. 3. Discuss the ionic structures based on radius ratio. 4. Predict the shapes of Pcl3, XeF4, Icl3 and Icl5 based on VSEPR theory. 5. Illustrate outer and inner orbital complexes based on valence bond theory. (DCHE 02) 6. Define stability constant. What are the various factors affecting stability of complexes? 7. Write notes on complementary and non-complementary reactions. 8. Discuss the classification and structures of silicates. PART B (4 x 15 = 60 marks) Answer ALL questions. 9. (a) Discuss the principle of L-S coupling, Predict the term symbol for the ground state of a d2 metal ion. Describe electron in a box with the help of quantum mechanics. 10. (a) What is LCAO? Describe the rules of LCAO. Explain the covalency in ionic compounds using Fajan s rules. 11. (a) Define Jahn-Teller effect. Explain the spectra of transition metal complexes using Jahn- Teller theorem. Draw orgel diagrams and predict the spectra of d 1 and d 8 metal complexes. 12. (a) Give the synthesis, properties and structures of phosphorus nitrogen cyclic compounds. Describe the ligand substitution reactions in octahedral complexes.
3 Time : Three hours M.Sc. (Previous) Chemistry DEGREE EXAMINATION, MAY 2007 Paper III - ORGANIC CHEMISTRY (DCHE 03) 1. Find out the aromaticity of the following compounds. (10) 2. Discuss the Stereospecific reaction with suitable examples. (10) 3. Explain the kinetic and thermodynamic control reactions with suitable examples (10) 4. What is SN 1 reaction? Explain the role of solvent with suitable examples. (10) 5. Write a short notes on the following reactions. (10) (a) Sandmayer reaction Hunsdecker reaction 6. Find out the products of the following reactions. (10)
4 7. Discuss the mechanism of the following reaction (10) (a) Stobbe condensation Benzoin condensation. 8. Product the products for the following reactions. (10) 3 PART B (4 x 15 = 60 marks) Answer ALL questions. 9. (a) Explain the hyper conjugation and cross conjugation with suitable examples. (10) Discuss the aromaticity of annulens. (5) (C) Explain the stereochemistry of Biphenyls and Allenes (15) 10. (a) Discuss the generation, structure, stability and reactivity of carbocations. (15) Discuss the generation, structure, stability and reactivity of Cabanions. (15) 11. (a) Write a short notes on : (15) (i) NBS (ii) Diazonium salts (iii) Auto-Oxidation Write a short notes on : (i) Hydroboration (ii) Micheal addition (iii) Birch reduction
5 12. (a) Discuss the mechanism of the following reactions. (15) (i) Witting reaction (ii) Perkin reaction (iii) Claisen condensation (i) Knovenagal reaction (ii) Mannich reaction (iii) Aldol reaction. Time : Three hours M.Sc. (Previous) Chemistry DEGREE EXAMINATION, MAY 2007 Paper IV - PHYSICAL CHEMISTRY 1. State Second Law of Thermodynamics. Describe Carnot cycle in detail. 2. Explain phase rule for sulphur system. 3. Describe the method of determining half life of a radio nuclide. 4. Explain the principle of Isotope dilution analysis. 5. What are semiconductors? Write few applications of semiconductors. 6. Define Fluorescence. Explain the factors that influence the phenomenon. 7. What is Adsorption Isotherm? Explain its significance. 8. what is cell e.m.f. and explain the method of measuring the cell e.m.f. PART B (4 x 15 = 60 marks) Answer all the FOUR questions 9. (a) Derive Gibbs-Helmholtz equation. Write few applications of this equation. (DCHE 04) State and explain Raoult s law. Explain the method of determining molecular weights by using this law. 10. (a) Write Bragg s equation and explain the terms involved in the equation. Explain the method of determining the crystal structure by this method. What are the important points to be followed while using radio tracers? Write the applications of radio tracers in agriculture and industry.
6 11. (a) Derive the kinetic equation for the first order reaction. Write few examples for first order reaction. Describe how the conductance of an electrolyte is measured? Draw the curve of equivalent conductance of a strong and weak electrolytes. 12. (a) What is catalyst? Explain theory of catalysis for homogeneous and heterogeneous reactions. State and explain the fundamental laws of photochemistry. Explain the photochemical decomposition reaction of Hydrogen Iodide. Time : Three hours M.Sc. (Final) Chemistry DEGREE EXAMINATION, MAY 2007 Paper V - ANALYTICAL CHEMISTRY 1. Describe the instrumentation of UV and visible spectrometer. 2. Describe the working principle and applications of Nephelometric titrations. (DCHE 21) 3. What factors will influence the fluorescence phenomenon and mention few applications of this technique? 4. What are interferences that occur in atomic absorption spectroscopy and explain how to overcome those interferences? 5. Describe the working and construction of dropping mercury electrode. Write the reactions at this electrode. 6. Explain the principle and applications of caulometric analysis. 7. Define distribution coefficient. What do you understand by batch extraction and continuous extraction? 8. Explain the component development in paper chromatography. How do you define R F value? PART B (4 x 15 = 60 marks) Answer all the FOUR questions 9. (a) Describe the methods of determining stability constant of complexes. Explain the function of acid-base indicator theory.
7 Describe the simultaneous determination of two metal ions by spectrophotometric method. Give any specific example. 10. (a) Explain the theory and instrumentation of phosphorimetry. Mention few applications of this technique. Explain the instrumentation of flame photometer. Write its working principle. Mention few applications of flame photometer. 11. (a) Explain the instrumentation and working of polarographic analyzer. Write few applications of this instrument. Describe the construction and working of hydrogen and calomel electrodes. Draw and explain the ph titration curve of sodium hydroxide and hydrochloric acid. 12. (a) Define Ion-exchange capacity. What are cation and anion exchangers? Write the applications of ion-exchangers in different fields. Describe the construction and working of high performance liquid chromatography (HPLC). What are the advantages in HPLC technique over GLC technique?
8 Time : Three hours M.Sc. (Final) Chemistry DEGREE EXAMINATION, MAY 2007 Paper VI - INORGANIC CHEMISTRY 1. Explain the synthesis of transuranium elements. 2. Give an account on the general properties of lanthanides. 3. Describe the magnetic properties of lanthanides. (DCHE 22) 4. Explain the experimental methods for the determination of magnetic moments of lanthanide complexes. 5. Describe the relation between intensity of transition to inorganic system. 6. Give an instrumentation and principle of IR spectroscopy. 7. Explain the mechanism of Oxygen transportation by Hemoglobin and myoglobin. 8. What is chemical shift? Explain the factors influence chemical shift. PART B (4 x 15 = 60 marks) Answer ALL questions. 9. (a) What is lanthanide contraction? How do you separate the lanthanides on the principle of lanthanide contraction? Write an essay on magnetic and spectral properties of lanthanides and actinides. 10. (a) How X-ray diffraction study explain the crystal structures and their properties? Write about the principle, instrumentation and applications of IR spectroscopy to inorganic system. 11. (a) Describe the spin-spin coupling and explain its applications to metal complexes and metal clusters. (i) Explain the hyperfine splitting with suitable examples. (ii) Give an account on Fragmentation pattern in mass spectroscopy. 12. (a) (i) Explain the mechanism of active transport across the membrane. (ii) Discuss the role of carboxy peptidase A and carbonic anhydrase in biological system. Write an account on Chelation therapy in metal toxicity and metal DNA interactions.
9 Time : Three hours M.Sc. (Final) Chemistry DEGREE EXAMINATION, MAY 2007 Paper VII - ORGANIC CHEMISTRY (DCHE 23) 1. (a) Write an short note on Franck Condon principle (5) Define the terms chromophors and auxochoroms and give examples. (5) 2. (a) What is the significance of Finger print region in IR spectrum. (5) Write about Fermi resonance. (5) 3. (a) Identify the non-equivalent protons in 2-methyl butanol (2) How many signals present in Aniline? (2) (c) Briefly explain Anisotropic effect. (6) 4. (a) How do representation mass spectrum? (5) Define spectroscopy. Write the basic principles in mass spectrum. (5) 5. Describe the different photophysical pathways involved in the deactivation of excited molecule through Jabalonski diagram. (10) 6. Write the correlation diagrams for (2 + 2) cycloaddition reaction. (10) 7. (a) How do synthesis Terebic acid from ethyl acetoacetate? (3) Define Isoprene rule. (2) (c) Write general isolation method for Terpenoids. (5) 8. Write mechanism for the following reactions : (5)
10 PART B ( 4 x 15 = 60 marks) Answer ALL questions. 9. (a) Write down the Woodward-Fieser rules for calculating absorption maxima of unsaturated carbonyl compounds. (10) Calculate the max for the following compounds (5) (c) Write the factors influencing on vibrational frequencies (10) (d) Write decreasing order of vibrational frequencies for the following compounds : (5) 10. (a) Define chemical shift in H NMR. (3) Write any two advantages for using TMS in H NMR spectrum (2) (c) Explain NOE effect. (10) (d) Explain metastable ion by using mass instrumentation. (10) (e) What are the fragmentation rules in mass spectrum. (5)
11 11. (a) Write the mechanism for the following reaction : (5) (c) Give an account on photocleavage reactions and give some examples. Define stereochemical modes of electrocyclic reactions and sigmatropic reactions.(5) (d) Explain FMO s method of (4n 2) e system. (10) 12. (a) Write the total synthesis of quinine. (10) Discuss about stereochemistry of morphine. (5) (c) Write a short notes on : (i) Favorskii rearrangement (5) (ii) Curtius rearrangement (5) (iii) Wagner-Meerwein rearrangement. (5) Time : Three hours M.Sc. (Final) Chemistry DEGREE EXAMINATION, MAY 2007 (DCHE 24) Paper VIII - ENVIRONMENTAL CHEMISTRY 1. Define and explain the Nomenclature of the environment. 2. Explain the formation of soil on the earth. 3. Explain the causes for the Air pollution. 4. Describe the importance of ozone layer. 5. Explain the nature of pollutants present in drinking water. 6. Explain the role of pesticides in the pollution. 7. Explain the determination of sulphur dioxide present in the air. 8. Explain the flash distillation process for water tratment.
12 PART B (4 x 15 = 60 marks) Answer al the FOUR question. 9. (a) Explain the formation of soil colloids. Discuss their ion-exchange properties in detail. Describe the determination total nitrogen content and moisture content in the soil. 10. (a) Describe the formation of different oxides of nitrogen and their analysis in the air samples. Describe how the aromatic hydrocarbons are analysed (as pollutants) in the air 11. (a) What are the pollutants present in Industrial effluents? Explain the analytical procedure for the determination of lead and arsenic. Describe the role of soaps and detergents and their effect with regard to water pollution. 12. (a) Describe the primary and secondary treatment methods of water. Discuss the working principles of monitoring instruments used in the determination of hydrogen sulfide and oxides of carbon.
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