COORDINATION CHEMISTRY, STATES OF MATTER & CHEMICAL KINETICS

Transition elements (3d series)-General group trends with special reference to electronic configuration, variable valency, colour, magnetic and catalytic properties, ability to form complexes and stability of various oxidation states (Latimer diagrams) for Mn, Fe and Cu.

Inner Transition Elements -Lanthanoids and actinoids: Electronic configurations, oxidation states, colour, magnetic properties, lanthanide contraction, separation of lanthanides (ion exchange method only).

Review of Werner’s coordination theory, concept of effective atomic number (EAN concept)

Classification of ligands, IUPAC nomenclature of coordination compounds. Isomerism in coordination compounds, structural isomerism and its types, stereochemistry of complexes of 4 and 6 coordination number, salient features of valence bond theory (VBT), structure of octahedral, tetrahedral and square planar complexes of Cr, Fe, Co, Ni and Cu on the basis of VBT and its limitations.

Crystal Field Theory- Important postulates, crystal field splitting of d-orbitals in octahedral and tetrahedral complexes, factors affecting the magnitude of Δ_0, calculation of crystal field stabilization energy, strong and weak ligands, spectrochemical series, distortion of octahedral complexes, crystal field splitting of d-orbitals in square planar complexes and Jahn Teller theorem. Use of CFSE values, number of unpaired electrons and high spin (HS) and low spin (LS) complexes, applications and limitations of CFT.

Postulates of kinetic theory of gases and derivation of the kinetic gas equation.

Deviation of real gases from ideal behaviour, compressibility factor, causes of deviation. Van der Waals equation of state for real gases. Boyle temperature (derivation not required). Law of corresponding states. Critical phenomena, critical constants and their calculation from van der Waals equation. Andrews isotherms of CO₂.

Maxwell Boltzmann distribution laws of molecular velocities and molecular energies (graphic representation – derivation not required) and their importance. Temperature dependence of these distributions. Most probable, average and root mean square velocities. Collision cross section, collision number, collision frequency, collision diameter and mean free path of molecules. Viscosity of gases, effect of temperature and pressure on coefficient of viscosity (qualitative treatment only).

Liquids: Characteristic properties of liquids: vapour pressure, surface tension, viscosity, refraction.  Surface tension and its determination using stalagmometer. Viscosity of a liquid and determination of coefficient of viscosity using Ostwald viscometer. Effect of temperature on surface tension and coefficient of viscosity of a liquid (qualitative treatment only). intermolecular forces

Solids : Forms of solids, unit cells, crystal systems, Bravais lattice types and identification of lattice planes. Laws of Crystallography- Law of constancy of interfacial angles, law of rational indices, symmetry elements, Miller indices. X-ray diffraction, Bragg’s law, a simple account of rotating crystal method and powder method, determination of crystal structure of NaCl, KCl and CsCl.

Defects in crystals, glasses and liquid crystals.

The concept of reaction rates, effect of temperature, pressure, catalyst and other factors on reaction rates, order and molecularity of a reaction, Integrated rate equations for zero, first and second order reactions (both for equal and unequal concentrations of reactants), half–life of a reaction, general methods for determination of order of a reaction.

Concept of activation energy and its calculation from Arrhenius equation.

Theories of reaction rates: Collision theory and activated complex theory of bimolecular reactions, comparison of the two theories (qualitative treatment only).