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Thermochemistry

Post author By Miraj Ahmad Ansari
Post date December 2, 2020

GATE CHEMISTRY Equilibrium Thermochemistry

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← Standard states → Thermodynamic functions and their relationships: Gibbs-Helmholtz and Maxwell relations, Gibbs-Duhem equation, van’t Hoff equation.

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December 2020

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Surfaces and Interfaces

5 Topics

Physisorption and chemisorption

Langmuir, Freundlich and Brunauer–Emmett–Teller (BET) isotherms

Surface catalysis: Langmuir-Hinshelwood mechanism

Surface tension, viscosity. Self-assembly

Physical chemistry of colloids, micelles and macromolecules

Main Group Elements

6 Topics

Hydrides, halides, oxides, oxoacids, nitrides, sulfides – shapes and reactivity

Structure and bonding of boranes, carboranes, silicones, silicates, boron nitride,borazines and phosphazenes

Allotropes of carbon, phosphorous and sulphur

Industrial synthesis of compounds of main group elements

Chemistry of noble gases, pseudohalogens,and interhalogen compounds.

Acid-base concepts and principles (Lewis, Brønsted, HSAB and acid-base catalysis).

Transition Elements: Coordination chemistry

5 Topics

structure and isomerism, theories of bonding (VBT, CFT, and MOT). Energy level diagrams in various crystal fields, CFSE, applications of CFT, Jahn-Teller distortion

Electronic spectra of transition metal complexes: spectroscopic term symbols, selection rules, Orgel and Tanabe-Sugano diagrams, nephelauxetic effect and Racah parameter, charge-transfer spectra

Magnetic properties of transition metal complexes

Ray-Dutt and Bailar twists, Reaction mechanisms: kinetic and thermodynamic stability,substitution and redox reactions

Metal-metal multiple bond

Lanthanides and Actinides

1 Topic

Recovery. Periodic properties, spectra and magnetic properties

13 Topics

Postulates of quantum mechanics. Operators.

Time dependent and time independent Schrödinger equations.

Born interpretation. Dirac bra-ket notation.

Particle in a box: infinite and finite square wells; concept of tunnelling; particle in 1D, 2D and 3D-box; applications.

Harmonic oscillator: harmonic and anharmonic potentials; hermite polynomials.

Rotational motion: Angular momentum operators, Rigid rotor.

Hydrogen and hydrogen-like atoms : atomic orbitals; radial distribution function.

Multi-electron atoms: orbital approximation; electron spin; Pauli exclusion principle; slater determinants.

Approximation Methods: Variation method and secular determinants; first order perturbation techniques.

Atomic units. Molecular structure and Chemical bonding: Born-Oppenheimer approximation;Valence bond theory and linear combination of atomic orbitals – molecular orbital (LCAO-MO) theory.

Hybrid orbitals.

Applications of LCAO-MO theory to H2+, H2; orbital theory (MOT) of homo- and heteronuclear diatomic molecules.

Hückel approximation and its application to annular π – electron systems.

1 Topic

Symmetry elements and operations; Point groups and character tables; Internal coordinates and vibrational modes; symmetry adapted linear combination of atomic orbitals (LCAO-MO); construction of hybrid orbitals using symmetry aspects

6 Topics

Atomic spectroscopy; Russell-Saunders coupling; Term symbols and spectral details; origin of selection rules.

Rotational, vibrational, electronic and Raman spectroscopy of diatomic and polyatomic molecules

Line broadening

Einstein’s coefficients.

Relationship of transition moment integral with molar extinction coefficient and oscillator strength.

Basic principles of nuclear magnetic resonance: gyromagnetic ratio; chemical shift, nuclear coupling.

21 Topics

Laws of thermodynamics

Standard states

Thermochemistry

Thermodynamic functions and their relationships: Gibbs-Helmholtz and Maxwell relations, Gibbs-Duhem equation, van’t Hoff equation.

Criteria of spontaneity and equilibrium. Absolute entropy.

Partial molar quantities

Thermodynamics of mixing

Chemical potential.

Fugacity, activity and activity coefficients.

Ideal and Non-ideal solutions, Raoult’s Law and Henry’s Law, Chemical equilibria.

Dependence of equilibrium constant on temperature and pressure.

Ionic mobility and conductivity. Debye-Hückel limiting law.

Debye-Hückel-Onsager equation

Standard electrode potentials and electrochemical cells

Nernst Equation and its application, relationship between Electrode potential and thermodynamic quantities, Potentiometric and conductometric titrations.

Clausius- Clapeyron equation

Phase diagram of one component systems: CO2, H2O, S; two component systems: liquid- vapour, liquid-liquid and solid-liquid systems

Fractional distillation

Azeotropes and eutectics

1 of 2

1 Topic

Elementary, parallel, opposing and consecutive reactions

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