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SYLLABUS
Chemistry-IV - BSc II Year IV Sem (2019-20)
Unit–I:
Inorganic Chemistry S4-I-1: Coordination Compounds –II Crystal field theory (CFT)- Postulates of CFT, splitting patterns of d-orbitals in ocahedral, tetrahedral, square planar with suitable examples. Crystalfield stabilization energies and its calculations for various dn configurations in octahedral complexes. High Spin Low Spin complexes. Colour and Magnetic properties of transition metal complexes. Calculations of magnetic moments spin only formula. Detection of complex formation - basic principles of various methods- change in chemical properties, solubility, colour, pH, conductivity, magnetic susceptibility. Hard and soft acids bases (HSAB) - Classification, Pearson’s concept of hardness and softness, application of HSAB principles – Stability of compounds / complexes, predicting the feasibility of reaction. Thermodynamic and kinetic stability of transition of metal complexes. Stability of metal complexes –stepwise and overall stability constant and their relationship and chelate effect, determination of composition of complex by Job’s method and mole ratio method. Applications of Coordination Compounds: Applications of coordination compounds (a) in quantitative and qualitative analysis with suitable examples (b) in medicine for removal of toxic metal ions and cancer therapy (c) in industry as catalysts polymerization – Ziegler Natta catalyst (d) water softening S4-I-2: Bioinorganic Chemistry Essential elements, biological significance of Na, K, Mg, Ca, Fe, Co, Ni, Cu, Zn and chloride (Cl- ). Toxic metal ions As, Hg & Pb Oxygen transport and storage – structure of hemoglobin, binding and transport of oxygen. Fixation of CO2 in photosynthesis- overview of light and dark reactions in photosynthesis. Structure of chlorophyll and coordination of magnesium. Electron transport in light reactions from water to NADP+ (Z – scheme).
Unit–II:
Organic Chemistry S4-O-1: Carbohydrates Introduction: Classification and nomenclature. Monosaccharides: All discussion to be confined to (+) glucose as an example of aldo hexoses and (-) fructose as example of ketohexoses. Chemical properties and structural elucidation: Evidences for straight chain pentahydroxy aldehyde structure. Number of optically active, isomers possible for the structure, configuration of glucose based on D-glyceraldehyde as primary standard (No proof for configuration is required). Evidence for cyclic structure of glucose (Pyranose structure, anomeric Carbon and anomers). Proof for the ring size (methylation, hydrolysis and oxidation reactions). (Haworth formula and chair conformational formula). Structure of fructose: Evidence of 2 – ketohexose structure. Same osazone formation from glucose and fructose, Hydrogen bonding in osazones, cyclic structure for fructose (Furanose structure,Haworth formula). Inter Conversion of Monosaccharides: Arabinose to D-glucose, D- mannose (kiliani – Fischer method). Epimers, Epimerisation- Lobry de bruyn van Ekenstein rearrangement. D-glucose to D-arabinose by Ruff’s degradation. Aldohexose(+) (glucose) to ketohexose (–) (fructose) and Ketohexose(Fructose) to aldohexose (Glucose) S4-O-2: Amino acids and proteins Classification. Methods of Synthesis: General methods of synthesis of alpha amino acids (specific examples – Glycine, Alanine, Valine and Leucine) by following methods: a) From halogenated Carboxylic acid b)Malonic ester synthesis c) strecker’s synthesis. Physical properties: Optical activity of naturally occurring amino acids. Zwitter ion structure – salt like character, definition of isoelectric point. Chemical properties: General reactions due to amino and carboxyl groups – Lactams from gamma and delta amino acids by heating peptide bond (amide linkage). Structure and nomenclature of peptides. Primary structure of proteins, di peptide synthesis S4-O-3: Heterocyclic Compounds Introduction and Definition: 5 membered ring compounds with one hetero atom Ex. Furan. Thiophene and pyrrole. Importance of ring systems –Numbering. Aromatic character. Resonance structures: Explanation of feebly acidic character of pyrrole, electrophillic substitution, Halogenation, Nitration and Sulphonation. Reactivity of furan as 1,3-diene, Diels Alder reactions (one example). Sulphonation of thiophene (purification of Benzene obtained from coal tar). Preparation of furan, Pyrrole and thiophene Paul-Knorr synthesis. Structure of pyridine, Basicity – Aromaticity – Comparison with pyrrole – preparation by Hantsch method and properties – Reactivity towards Nucleophilic substitution reaction – chichibabin reaction.
Unit–III:
Physical Chemistry S4-P-1: Chemical Kinetics Introduction to chemical kinetics, rate of reaction, variation of concentration with time, rate laws and rate constant. Specific reaction rate. Factors influencing reaction rates: effect of concentration of reactants, effect of temperature, effect of pressure, effect of reaction medium, effect of radiation, effect of catalyst with simple examples. Order of a reaction. First order reaction, derivation of equation for rate constant. Characteristics of first order reaction. Units for rate constant. Half- life period, graph of first order reaction, Examples-Decomposition of H2 O2 and decomposition of oxalic acid, Problems. Pseudo first order reaction, Hydrolysis of methyl acetate, inversion of cane sugar, problems. Second order reaction, derivation of expression for second order rate constant, examples Saponification of ester, 2O3 → 3O2 , C2 H4 +H2 → C2 H6 . Characteristics of second order reaction, units for rate constants, half- life period and second order plots. Problems S4-P-2: Photochemistry Introduction to photochemical reactions, Difference between thermal and photochemical reactions, Laws of photo chemistry- Grotthus Draper law, Stark–Einstein’s Law of photochemical equivalence. Quantum yield. Examples of photo chemical reactions with different quantum yields. Photo chemical combinations of H2 –Cl2 and H2 –Br2 reactions, reasons for the high and low quantum yield. Problems based on quantum efficiency. Consequences of light absorption. Singlet and triplet states. Jablonski diagram. Explanation of internal conversion, inter- system crossing, phosphorescence, fluorescence.
Unit–IV:
General Chemistry S4-G-1: Theories of bonding in metals Valence bond theory, Explanation of metallic properties and its limitations, Free electron theory, thermal and electrical conductivity of metals, limitations, Band theory, formation of bands, explanation of conductors, semiconductors n-type and p-type, extrinsic & intrinsic semiconductors, and insulators. S4-G-2: Carbanions-II Mannich reaction , Michael addition and Knoevengeal condensation Synthetic applications of Aceto acetic ester. Acid hydrolysis and ketonic hydrolysis: Preparation of ketones, monocarboxylic acids and dicarboxylic acids Malonic ester– synthetic applications. Preparation of (i) substituted mono carboxylic acids and (ii) substituted dicarboxylic acids. S4-G-3: Colloids & Surface Chemistry Definition of colloids. Classification of colloids. Solids in liquids (sols): preparations and properties – Kinetic, Optical and Electrical stability of colloids. Protective action. Hardy– Schultz law, Gold number. Liquids in liquids (emulsions): Types of emulsions, preparation and emulsifier. Liquids in solids(gels): Classification, preparations and properties, General applications of colloids. Adsorption:Types of adsorption. Factors influencing adsorption. Freundlich adsorption isotherm. Langmuir theory of unilayer adsorption isotherm. Applications.
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