Syllabus /

Mains Chemistry Paper-I

For the posts of Chemist and Scientist ‘B’(Chemical)
Stage-II Mains (Descriptive Type)
Chemistry : Paper-I (Inorganic Chemistry)

1. Inorganic solids:

Defects, non-stoichiometric compounds and solid solutions, atom and ion diffusion, solid electrolytes. Synthesis of materials, monoxides of 3d-metals, higher oxides, complex oxides (corundrum, ReO3, spinel, pervoskites), framework structures (phosphates, aluminophosphates, silicates, zeolites), nitrides and fluorides, chalcogenides, intercalation chemistry, semiconductors, molecular materials.

2. Chemistry of coordination compounds:

Isomerism, reactivity and stability: Determination of configuration of cis- and trans- isomers by chemical methods. Labile and inert complexes, substitution reactions on square planar complexes, trans effect. Stability constants of coordination compounds and their importance in inorganic analysis.

Structure and bonding: Elementary Crystal Field Theory: splitting of dn configurations in octahedral, square planar and tetrahedral fields, crystal field stabilization energy, pairing energy. Jahn-Teller distortion. Metal-ligand bonding, sigma and pi bonding in octahedral complexes and their effects on the oxidation states of transition metals. Orbital and spin magnetic moments, spin only moments and their correlation with effective magnetic moments, d-d transitions; LS coupling, spectroscopic ground states, selection rules for electronic spectral transitions; spectrochemical series of ligands, charge transfer spectra.

3. Acid base titrations:

Titration curves for strong acid-strong base, weak acid-strong base and weak base-strong acid titrations, polyprotic acids, poly-equivalent bases, determining the equivalence point: theory of acidbase indicators, pH change range of indicator, selection of proper indicator. Principles used in estimation of mixtures of NaHCO3 and Na2CO3 (by acidimetry).

4. Gravimetric Analysis:

General principles: Solubility, solubility product and common ion effect, effect of temperature on the solubility; Salt hydrolysis, hydrolysis constant, degree of hydrolysis. Stoichiometry, calculation of results from gravimetric data. Properties of precipitates. Nucleation and crystal growth, factors influencing completion of precipitation. Co-precipitation and post- precipitation, purification and washing of precipitates. Precipitation from homogeneous solution. A few common gravimetric estimations: chloride as silver chloride, sulphate as barium sulphate, aluminium as oxinate and nickel as dimethyl glyoximate.

5. Redox Titrations:

Standard redox potentials, Nernst equation. Influence of complex formation, precipitation and change of pH on redox potentials, Normal Hydrogen Electrode (NHE). Feasibility of a redox titration, redox potential at the equivalence point, redox indicators. Redox potentials and their applications. Principles behind Iodometry, permanganometry, dichrometry, difference between iodometry and iodimetry. Principles of estimation of iron, copper, manganese, chromium by redox titration.

6. Complexometric titrations:

Complex formation reactions, stability of complexes, stepwise formation constants, chelating agents. EDTA: acidic properties, complexes with metal ions, equilibrium calculations involving EDTA, conditional formation constants, derivation of EDTA titration curves, effect of other complexing agents, factors affecting the shape of titration curves: indicators for EDTA titrations, titration methods employing EDTA: direct, back and displacement titrations, indirect determinations, titration of mixtures, selectivity, masking and demasking agents. Typical applications of EDTA
titrations: hardness of water, magnesium and aluminium in antacids, magnesium, manganese and zinc in a mixture, titrations involving unidentate ligands: titration of chloride with Hg2+ and cyanide with Ag+.

7. Organometallic compounds:

18-electron rule and its applications to carbonyls and nature of bonding involved therein. Simple examples of metal-metal bonded compounds and metal clusters. Wilkinson’s catalyst.

8. Nuclear chemistry:

Radioactive decay- General characteristics, decay kinetics, parent-daughter decay growth relationships, determination of half-lives. Nuclear stability. Decay theories. Unit of radioactivity. Preparation of artificial radionuclides by bombardment, radiochemical separation techniques. Experimental techniques in the assay of radioisotopes, Geiger-Muller counters. Solid state detectors.

9. Chemistry of d- and f-block elements:

d-block elements: General comparison of 3d, 4d and 5d elements in terms of electronic configuration, elemental forms, metallic nature, atomization energy, oxidation states, redox properties, coordination chemistry, spectral and magnetic properties. f-block elements: Electronic configuration, ionization enthalpies, oxidation states, variation in atomic and ionic (3+) radii, magnetic and spectral properties of lanthanides, separation of lanthanides (by ion-exchange method).

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