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Free energy functions

Post author By Miraj Ahmad Ansari
Post date December 11, 2020

UPSC Chemistry Thermodynamics Free energy functions

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← entropy-reversibility and irreversibility → Thermodynamic equation of state

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PAPER 1

Atomic Structure

2 Topics

Heisenberg’s uncertainty principle, Schrodinger wave equation (time-independent)

Interpretation of wave function, particle in one-dimensional box, quantum numbers, hydrogen atom wave functions; Shapes of s, p and d orbitals

Chemical Bonding

11 Topics

characteristics of ionic compounds

lattice energy, Born-Haber cycle

covalent bond and its general characteristics

polarities of bonds in molecules and their dipole moments

Valence bond theory

concept of resonance and resonance energy

Molecular orbital theory (LCAO method)

bonding in H2+, H2, He2+ to Ne2, NO, CO, HF, and CN-

Comparison of valence bond and molecular orbital theories

bond order, bond strength and bond length.

7 Topics

Crystal systems

Designation of crystal faces, lattice structures and unit cell

X-ray diffraction by crystals

Close packing, radius ratio rules, calculation of some limiting radius ratio values

Structures of NaCl, ZnS, CsCl and CaF2

Stoichiometric and nonstoichiometric defects, impurity defects, semi-conductors

The Gaseous State and Transport Phenomenon

6 Topics

Equation of state for real gases

intermolecular interactions and critical phenomena and liquefaction of gases

Maxwell’s distribution of speeds

intermolecular collisions

collisions on the wall and effusion

Thermal conductivity and viscosity of ideal gases

4 Topics

Kelvin equation

Surface tension and surface energy

wetting and contact angle

interfacial tension and capillary action

12 Topics

Work, heat and internal energy

first law of thermodynamics

Second law of thermodynamics

entropy as a state function

entropy changes in various processes

entropy-reversibility and irreversibility

Free energy functions

Thermodynamic equation of state

Maxwell relations

Temperature, volume and pressure dependence of U, H, A, G, Cp and Cv α and β; J-T effect and inversion temperature

criteria for equilibrium, relation between equilibrium constant and thermodynamic quantities

Nerns theat theorem, introductory idea of third law of thermodynamics

Phase Equilibria and Solutions

5 Topics

Clausius-Clapeyron equation

phase diagram for a pure substance

phase equilibria in binary systems, partially miscible liquids-upper and lower critical solution temperatures

partial molar quantities, their significance and determination

excess thermodynamic functions and their determination

Electrochemistry

8 Topics

Debye-Huckel theory of strong electrolytes and Debye-Huckel limiting Law for various equilibrium and transport properties

Galvanic cells, concentration cells

electrochemical series, measurement of e.m.f. of cells and its applications fuel cells and batteries

Processes at electrodes

double layer at the interface

rate of charge transfer, current density; overpotential

electro-analytical techniques

Polarography, amperometry, ion selective electrodes and their uses

Chemical Kinetics

6 Topics

Differential and integral rate equations for zeroth, first, second and fractional order reactions

Rate equations involving reverse, parallel, consecutive and chain reactions

branching chain and explosions

effect of temperature and pressure on rate constant

Study of fast reactions by stop-flow and relaxation methods

Collisions and transition state theories

3 Topics

Absorption of light

decay of excited state by different routes

photochemical reactions between hydrogen and halogens and their quantum yields

Surface Phenomena and Catalysis

2 Topics

Absorption from gases and solutions on solid adsorbents, Langmuir and B.E.T. adsorption isotherms

determination of surface area, characteristics and mechanism of reaction on heterogeneous catalysts

Bio-inorganic Chemistry

2 Topics

Metal ions in biological systems and their role in ion transport across the membranes (molecular mechanism)

oxygenuptake proteins, cytochromes and ferredoxins

Coordination Compounds

13 Topics

Bonding theories of metal complexes

Valence bond theory, crystal field theory and its modifications

applications of theories in the explanation of magnetism and electronic spectra of metal complexes

Isomerism in coordination compounds

IUPAC nomenclature of coordination compounds

stereochemistry of complexes with 4 and 6 coordination numbers

chelate effect and polynuclear complexes

trans effect and its theories

kinetics of substitution reactions in square-planer complexes; thermodynamic and kinetic stability of complexes

EAN rule, Synthesis structure and reactivity of metal carbonyls

carboxylate anions, carbonyl hydrides and metal nitrosyl compounds

Complexes with aromatic systems, synthesis, structure and bonding in metal olefin complexes, alkyne complexes and cyclopentadienyl complexes

coordinative unsaturation, oxidative addition reactions, insertion reactions, fluxional molecules and their characterization; Compounds with metal-metal bonds and metal atom clusters

Main Group Chemistry

2 Topics

Boranes, borazines, phosphazenes and cyclic phosphazene, silicates and silicones, Interhalogen compounds

Sulphur – nitrogen compounds, noble gas compounds

General Chemistry of 'f' Block Elements

2 Topics

Lanthanides and actinides

separation, oxidation states, magnetic and spectral properties; lanthanide contraction

PAPER 2

Delocalised Covalent Bonding

1 Topic

Aromaticity, anti-aromaticity; annulenes, azulenes, tropolones, fulvenes, sydnones.

Reaction Mechanisms

3 Topics

General methods (both kinetic and non-kinetic) of study of mechanism of organic reactions

isotopic method, cross-over experiment, intermediate trapping, stereochemistry; energy of activation

thermodynamic control and kinetic control of reactions.

Reactive Intermediates

1 Topic

Generation, geometry, stability and reactions of carbonium ions and carbanions, free radicals, carbenes, benzynes and nitrenes

Substitution Reactions

3 Topics

SN1, SN2 and SNi mechanisms

neighbouring group participation

electrophilic and nucleophilic reactions of aromatic compounds including heterocyclic compounds-pyrrole, furan, thiophene and indole

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