Exam

Exam

GATE: CHEMISTRY Syllabus

CY Chemistry

Section 1: Physical Chemistry

Structure: Postulates of quantum mechanics. Time dependent and time independent

Schrödinger equations. Born interpretation. Particle in a box. Harmonic oscillator. Rigid

rotor. Hydrogen atom: atomic orbitals. Multi-electron atoms: orbital approximation.

Variation and first order perturbation techniques. Chemical bonding: Valence bond

theory and LCAO-MO theory. Hybrid orbitals. Applications of LCAO-MOT to H2+, H2 and

other homonuclear diatomic molecules, heteronuclear diatomic molecules like HF, CO,

NO, and to simple delocalized π– electron systems. Hückel approximation and its

application to annular π – electron systems. Symmetry elements and operations. Point

groups and character tables. Origin of selection rules for rotational, vibrational, electronic

and Raman spectroscopy of diatomic and polyatomic molecules. Einstein coefficients.

Relationship of transition moment integral with molar extinction coefficient and oscillator

strength. Basic principles of nuclear magnetic resonance: nuclear g factor, chemical shift,

nuclear coupling.

Equilibrium: Laws of thermodynamics. Standard states. Thermochemistry. Thermodynamic

functions and their relationships: Gibbs-Helmholtz and Maxwell relations, van’t Hoff

equation. Criteria of spontaneity and equilibrium. Absolute entropy. Partial molar

quantities. Thermodynamics of mixing. Chemical potential. Fugacity, activity and activity

coefficients. Chemical equilibria. Dependence of equilibrium constant on temperature

and pressure. Non-ideal solutions. Ionic mobility and conductivity. Debye-Hückel limiting

law. Debye-Hückel-Onsager equation. Standard electrode potentials and

electrochemical cells. Potentiometric and conductometric titrations. Phase rule. 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. Statistical thermodynamics: microcanonical and

canonical ensembles, Boltzmann distribution, partition functions and thermodynamic

properties.

Kinetics: Transition state theory: Eyring equation, thermodynamic aspects. Potential

energy surfaces and classical trajectories. Elementary, parallel, opposing and consecutive

reactions. Steady state approximation. Mechanisms of complex reactions. Unimolecular

reactions. Kinetics of polymerization and enzyme catalysis. Fast reaction kinetics:

relaxation and flow methods. Kinetics of photochemical and photophysical processes.

Surfaces and Interfaces: Physisorption and chemisorption. Langmuir, Freundlich and BET

isotherms. Surface catalysis: Langmuir-Hinshelwood mechanism. Surface tension, viscosity.

Self-assembly. Physical chemistry of colloids, micelles and macromolecules.

Section 2: Inorganic Chemistry

Main Group Elements: 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. Chemistry of noble gases,

pseudohalogens, and interhalogen compounds. Acid-base concepts.

Transition Elements: Coordination chemistry – 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 diagrams, charge-transfer spectra. Magnetic

properties of transition metal complexes. Reaction mechanisms: kinetic and

thermodynamic stability, substitution and redox reactions.

Lanthanides and Actinides: Recovery. Periodic properties, spectra and magnetic

properties.

Organometallics: 18-Electron rule; metal-alkyl, metal-carbonyl, metal-olefin and metal-
carbene complexes and metallocenes. Fluxionality in organometallic complexes. Types of

organometallic reactions. Homogeneous catalysis - Hydrogenation, hydroformylation,

acetic acid synthesis, metathesis and olefin oxidation. Heterogeneous catalysis - Fischer-
Tropsch reaction, Ziegler-Natta polymerization.

Radioactivity: Decay processes, half-life of radioactive elements, fission and fusion

processes.

Bioinorganic Chemistry: Ion (Na+ and K+) transport, oxygen binding, transport and

utilization, electron transfer reactions, nitrogen fixation, metalloenzymes containing

magnesium, molybdenum, iron, cobalt, copper and zinc.

Solids: Crystal systems and lattices, Miller planes, crystal packing, crystal defects, Bragg’s

law, ionic crystals, structures of AX, AX2, ABX3 type compounds, spinels, band theory,

metals and semiconductors.

Instrumental Methods of Analysis: UV-visible spectrophotometry, NMR and ESR

spectroscopy, mass spectrometry. Chromatography including GC and HPLC.

Electroanalytical methods- polarography, cyclic voltammetry, ion-selective electrodes.

Thermoanalytical methods.

Section 3: Organic Chemistry

Stereochemistry: Chirality of organic molecules with or without chiral centres and

determination of their absolute configurations. Relative stereochemistry in compounds

having more than one stereogenic centre. Homotopic, enantiotopic and diastereotopic

atoms, groups and faces. Stereoselective and stereospecific synthesis. Conformational

analysis of acyclic and cyclic compounds. Geometrical isomerism. Configurational and

conformational effects, and neighbouring group participation on reactivity and

selectivity/specificity.

Reaction Mechanisms: Basic mechanistic concepts – kinetic versus thermodynamic

control, Hammond’s postulate and Curtin-Hammett principle. Methods of determining

reaction mechanisms through identification of products, intermediates and isotopic

labeling. Nucleophilic and electrophilic substitution reactions (both aromatic and

aliphatic). Addition reactions to carbon-carbon and carbon-heteroatom (N,O) multiple

bonds. Elimination reactions. Reactive intermediates – carbocations, carbanions,

carbenes, nitrenes, arynes and free radicals. Molecular rearrangements involving electron

deficient atoms.

Organic Synthesis: Synthesis, reactions, mechanisms and selectivity involving the following

classes of compounds – alkenes, alkynes, arenes, alcohols, phenols, aldehydes, ketones,

carboxylic acids, esters, nitriles, halides, nitro compounds, amines and amides. Uses of Mg,

Li, Cu, B, Zn and Si based reagents in organic synthesis. Carbon-carbon bond formation

through coupling reactions - Heck, Suzuki, Stille and Sonogoshira. Concepts of multistep

synthesis - retrosynthetic analysis, strategic disconnections, synthons and synthetic

equivalents. Umpolung reactivity – formyl and acyl anion equivalents. Selectivity in

organic synthesis – chemo-, regio- and stereoselectivity. Protection and deprotection of

functional groups. Concepts of asymmetric synthesis – resolution (including enzymatic),

desymmetrization and use of chiral auxilliaries. Carbon-carbon bond forming reactions

through enolates (including boron enolates), enamines and silyl enol ethers. Michael

addition reaction. Stereoselective addition to C=O groups (Cram and Felkin-Anh models).

Pericyclic Reactions and Photochemistry: Electrocyclic, cycloaddition and sigmatropic

reactions. Orbital correlations - FMO and PMO treatments. Photochemistry of alkenes,

arenes and carbonyl compounds. Photooxidation and photoreduction. Di-π-methane

rearrangement, Barton reaction.

Heterocyclic Compounds: Structure, preparation, properties and reactions of furan,

pyrrole, thiophene, pyridine, indole, quinoline and isoquinoline.

Biomolecules: Structure, properties and reactions of mono- and di-saccharides,

physicochemical properties of amino acids, chemical synthesis of peptides, structural

features of proteins, nucleic acids, steroids, terpenoids, carotenoids, and alkaloids.

Spectroscopy: Applications of UV-visible, IR, NMR and Mass spectrometry in the structural

determination of organic molecules.

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