Kerala PSC Work Assistant (Kerala Ceramics) Syllabus 2022

Date

Principle, Schrödinger’s wave equation, Quantum numbers and their significance, Shapes of s, p, d

and f orbitals. Pauli’s Exclusion Principle, Hund’s rule of maximum multiplicity, Aufbau’s principle,

Variation of orbital energy with atomic number, s, p, d, f block elements and their properties.

Shielding effect, Slater rules, variation of effective nuclear charge in periodic table. Ionization

enthalpy, factors affecting ionization energy, applications of ionization enthalpy. Electron gain

enthalpy, trends of electron gain enthalpy. Electronegativity, Pauling’s/ Mulliken’s and Allred

Rachow’s electronegativity scales, hybridization, Inert pair effect, relative stability of different

oxidation states, diagonal relationship and anomalous behaviour of first member of each group.

Structure, bonding, preparation, properties and uses of boric acid and borates, boron nitrides,

borohydrides (diborane), carboranes, silanes, Oxides and oxoacids of nitrogen, phosphorus and

chlorine, Peroxo acids of sulphur, interhalogen compounds, polyhalide ions, pseudohalogens and

basic properties of halogens. Occurrence and uses of noble gases, clathrates; preparation and

properties of XeF2, XeF4 and XeF6.

Radius ratio rule, Born-Haber cycle and its application, Solvation energy. Lewis structure, valence

bond theory, resonance and resonance energy, Molecular orbital theory. Molecular orbital diagrams

of diatomic and simple polyatomic molecules N2, O2, C2, B2, F2, CO, NO, and their ions; Formal

charge, Valence shell electron pair repulsion theory (VSEPR), shapes of simple molecules and ions

containing lone pairs and bond pairs of electrons, Covalent character in ionic compounds, polarizing

power and polarizability. Fajan’s rules and consequences of polarization. Ionic character in covalent

compounds: Bond moment and dipole moment. Percentage ionic character from dipole moment and

electronegativity difference. Semiconductors and insulators, defects in solids. van der Waals forces,

Hydrogen bonding and its effects on melting and boiling points, solubility and energy of

the dissolution process.

compounds. Stereochemistry of complexes with 4 and 6 coordination numbers. Chelate effect,

valence bond theory (inner and outer orbital complexes), back bonding. Crystal field theory, CFSE in

weak and strong fields, pairing energies, factors affecting the magnitude of 10 Dq (Δo, Δt).

Octahedral vs. tetrahedral coordination, tetragonal distortions from octahedral geometry Jahn-Teller

theorem, square planar geometry. The qualitative aspect of Ligand field and MO Theory. Substitution

reactions in square planar complexes, Trans- effect, mechanism of nucleophilic substitution in

square planar complexes, Thermodynamic and Kinetic stability, Kinetics of octahedral

substitution, Ligand field effects and reaction rates, Mechanism of substitution in octahedral

complexes.

Chief modes of occurrence of metals, electrolytic Reduction, hydrometallurgy, methods of

purification of metals: Electrolytic, Kroll process, van Arkel and Mond’s process, Zone refining.

Metal ions present in biological systems, classification of elements according to their action in

a biological system. Sodium / K-pump, carbonic anhydrase and carboxypeptidase. Excess and

deficiency of some trace metals. Toxicity of metal ions (Hg, Pb, Cd and As), reasons for toxicity, Use

of chelating agents in medicine. Iron and its application in bio-systems, Haemoglobin; Storage and

transfer of iron.

ligands. Metal carbonyls: 18 electron rule, electron count of mononuclear, polynuclear and substituted

metal carbonyls of 3d series. General methods of preparation (direct combination, reductive

carbonylation, thermal and photochemical decomposition) of mono and binuclear carbonyls of 3d

series. Structures of mononuclear and binuclear carbonyls of Cr, Mn, Fe, Co and Ni using VBT. –

acceptor behaviour of CO, synergic effect and use of IR data to explain the extent of back bonding.

Zeise’s salt: Preparation and structure.

Metal Alkyls: Important structural features of methyl lithium (tetramer) and trialkyl aluminium

(dimer), the concept of multicentre bonding in these compounds. Role of triethylaluminium in

polymerisation of ethene (Ziegler – Natta Catalyst). Ferrocene: Preparation and reactions (acetylation,

alkylation, metallation, Mannich Condensation). Structure and aromaticity. Comparison of

aromaticity and reactivity with that of benzene. Mechanism of Alkene hydrogenation (Wilkinsons

Catalyst), Hydroformylation (Co salts), Wacker Process, Synthetic gasoline (Fischer Tropsch

reaction).

statistical test of data; F, Q and t-test

Basic principles involved in the analysis of cations and anions and solubility products, common ion

effect. Principles involved in the separation of cations into groups and choice of group reagents.

Interfering anions (fluoride, borate, oxalate and phosphate) and need to remove them after Group II.

Flame Atomic Absorption and Emission Spectrometry: Basic principles, Techniques of atomization

and sample introduction; sources of chemical interferences and their method of removal. Techniques

for the quantitative estimation of trace level of metal ions from samples. Classification of

electroanalytical methods, the basic principle of pH metric, potentiometric and conductometric titrations.

Techniques used for the determination of pKa values. Theory of thermogravimetry (TG), Techniques

for quantitative estimation of Ca and Mg from their mixture. Complexometric titration: EDTA

titration.

resonance and mesomeric effects, hyperconjugation and their applications. Organic acids and bases;

their relative strength. Homolytic and heterolytic fission, electrophiles and nucleophiles; Types, shape

and their relative stability of carbocations, carbanions, free radicals and carbenes. Introduction to

types of organic reactions and their mechanism: Addition, Elimination and Substitution reactions.

Fischer Projection, Newmann and Sawhorse Projection formulae and their interconversions;

Geometrical isomerism: cis-trans and, syn-anti isomerism E/Z notations with C.I.P rules. Optical

Isomerism: Optical Activity, Specific Rotation, Chirality/Asymmetry, Enantiomers, Molecules with

two or more chiral-centres, Distereoisomers, mesostructures, Racemic mixture and resolution.

Relative and absolute configuration: D/L and R/S designations.

Applications of IR, UV and NMR for identification of simple organic molecules.

Halogenation-relative reactivity and selectivity. Formation of alkenes and alkynes by elimination

reactions, Mechanism of E1, E2, E1cb reactions. Saytzeff and Hofmann eliminations. Reactions of

alkenes: Electrophilic additions their mechanisms (Markownikoff/ Anti Markownikoff addition),

mechanism of oxymercuration-demercuration, hydroboration-oxidation, ozonolysis, reduction

(catalytic and chemical), syn and anti-hydroxylation (oxidation), 1,2 and 1,4-addition reactions in

conjugated dienes, Diels-Alder reaction; Allylic and benzylic bromination and mechanism, Reactions

of alkynes: Acidity, Electrophilic and Nucleophilic additions. Hydration to form carbonyl compounds,

Alkylation of terminal alkynes. Types of cycloalkanes and their relative stability, Baeyer strain theory,

Conformation analysis of alkanes and cyclohexane.

mechanisms with stereochemical aspects and effect of solvent etc.; nucleophilic substitution vs.

elimination.

Aryl halides: Methods of reparation, nucleophilic aromatic substitution; SNAr, Benzyne mechanism.

Relative reactivity of alkyl, allyl/benzyl, vinyl and aryl halides towards nucleophilic substitution

reactions. Organometallic compounds of Mg and Li – use in the synthesis of organic compounds.

Classification and nomenclature, Structure, aromaticity in 5-numbered and 6-membered rings

containing one heteroatom; Synthesis, reactions and mechanism of substitution reactions of Furan,

Pyrrole (Paal-Knorr synthesis, Knorr pyrrole synthesis, Hantzsch synthesis), Thiophene, Pyridine

(Hantzsch synthesis), Pyrimidine, Skraup synthesis, Friedlander’s synthesis, Knorr quinoline

synthesis, Bischler-Napieralski reaction Derivatives of furan: Furfural and furoic acid.

, 2°, 3° alcohols, Bouvaelt-Blanc

Reduction; Preparation and properties of glycols: Oxidation by periodic acid and lead tetraacetate,

Pinacol-Pinacolone rearrangement.

Phenols: Preparation and properties; Acidity and factors affecting it, Ring substitution reactions,

Reimer–Tiemann and Kolbe’s–Schmidt Reactions, Fries and Claisen rearrangements with

mechanism.

Ethers and Epoxides: Preparation and reactions with acids. Reactions of epoxides with alcohols,

ammonia derivatives and LiAlH4

Preparation and important reactions of nitro compounds, nitriles, isonitriles and amines: Effect of

substituent and solvent on the basicity of amines; Gabriel phthalimide synthesis, Carbylamine reaction,

Mannich reaction, Hoffmann’s exhaustive methylation, Hofmann-elimination reaction; Distinction

between 1°, 2° and 3° amines with Hinsberg reagent and nitrous acid. Diazonium Salts: Preparation

and their synthetic applications.

addition-elimination reactions with ammonia derivatives. Mechanisms of Aldol and Benzoin

condensation, Knoevenagel condensation, Claisan-Schmidt, Perkin, Cannizzaro and Wittig reaction,

Beckmann and Benzil-Benzilic acid rearrangements, haloform reaction and Baeyer Villiger oxidation,

α- substitution reactions, oxidations and reductions (Clemmensen, Wolff-Kishner, LiAlH4, NaBH4,

MPV), Michael addition. Active methylene compounds: Keto-enol tautomerism. Preparation and

synthetic applications of diethyl malonate and ethyl acetoacetate. Preparation, physical properties and

reactions of monocarboxylic acids. Typical reactions of dicarboxylic acids, hydroxy acids and

unsaturated acids: succinic/phthalic, lactic, malic, tartaric, citric, maleic and fumaric acids.

Preparation and reactions of acid chlorides, anhydrides, esters and amides; Comparative study of

nucleophilic substitution at acyl group -Mechanism of acidic and alkaline hydrolysis of esters, Claisen

condensation, Dieckmann and Reformatsky reactions, Hofmann- bromamide degradation and Curtius

rearrangement.

the relation between mean free path and coefficient of viscosity, variation of viscosity with temperature

and pressure. Maxwell distribution and its use in evaluating molecular velocities (average, root mean

square and most probable), the law of equipartition of energy, degrees of freedom and molecular basis of

heat capacities. The behaviour of real gases: Deviations from ideal gas behaviour, compressibility factor,

Z, and its variation with pressure for different gases. van der Waals equation of state, virial equation

of state; van der Waals equation expressed in virial form and calculation of Boyle temperature.

Isotherms of real gases and their comparison with van der Waals isotherms, continuity of states,

critical state, the relation between critical constants and van der Waals constants, the law of corresponding

states. physical properties of liquids; vapour pressure, surface tension and coefficient of viscosity, and

their determination. Effect of addition of various solutes on surface tension and viscosity. The cleansing

action of detergents. Temperature variation of viscosity of liquids and comparison with that of gases.

Nature of the solid-state, law of constancy of interfacial angles, the law of rational indices, Miller indices,

elementary ideas of symmetry, symmetry elements and symmetry operations, the qualitative idea of point

and space groups, seven crystal systems and fourteen Bravais lattices; X-ray diffraction, Bragg’s law,

Analysis of powder diffraction patterns of NaCl, CsCl and KCl. Defects in crystals. Glasses and

liquid crystals.

water. Ionization of weak acids and bases, pH scale, common ion effect, dissociation constants of

mono-, di-and tricrotic acids. Salt hydrolysis-calculation of hydrolysis constant, degree of hydrolysis

and pH for different salts. Buffer solutions, Henderson equation and its applications, buffer capacity,

buffer action and applications of buffers in analytical chemistry and biochemical processes in the

human body. Solubility and solubility product of sparingly soluble salts – applications of solubility

product principle. Qualitative treatment of acid-base titration curves (calculation of pH at various

stages). Theory of acid-base indicators; selection of indicators and their limitations. Criteria of

thermodynamic equilibrium, chemical equilibria in ideal gases, the concept of fugacity. Thermodynamic

relation between Gibbs free energy of reaction and reaction quotient. Equilibrium constants and their

quantitative dependence on temperature, pressure and concentration. Free energy of mixing and

spontaneity; relations between the various equilibrium constants Kp, Kc and Kx. Le Chatelier principle.

Concept of phases, components and degrees of freedom, Clausius-Clapeyron equation and its

applications to solid-liquid, liquid-vapour and solid-vapour equilibria, the phase diagram for one-component systems, with applications. Phase diagrams for systems of solid-liquid equilibria involving

eutectic, congruent and incongruent melting points, solid solutions. Three-component systems, water chloroform-acetic acid system Binary solutions: Gibbs-Duhem-Margules equation and its applications

to a fractional distillation of binary miscible liquids (ideal and nonideal), azeotropes, partial miscibility

of liquids, CST, miscible pairs, steam distillation. Nernst distribution law and its applications Dilute

solutions, lowering of vapour pressure, Raoult’s and Henry’s Laws and their applications.

Applications of relative lowering of vapour pressure, the elevation of boiling point, depression of

freezing point and osmotic pressure in calculating molar masses of solutes in solution.

law of thermodynamics. Concept of heat (q), work(w), internal energy (U) and statement of the first law,

enthalpy (H), the relation between heat capacities, calculations of q, w, U and H for reversible,

irreversible and free expansion of gases (ideal and van der Waals) under isothermal and adiabatic

conditions. Heats of reactions: standard states; enthalpy of formation of molecules and ions and

enthalpy of combustion and its applications; calculation of bond energy, bond dissociation energy and

resonance energy from thermochemical data, the effect of temperature (Kirchhoff’s equations) and

pressure on the enthalpy of reactions. Concept of entropy; the thermodynamic scale of temperature, statement

of the second law of thermodynamics. Calculation of entropy change for reversible and irreversible

processes. Statement of third law, the concept of residual entropy, calculation of absolute entropy of

molecules. Gibbs and Helmholtz energy; variation of S, G, A with T, V, P; Free energy change and

spontaneity. Relation between Joule-Thomson coefficient and other thermodynamic parameters;

inversion temperature; Gibbs-Helmholtz equation; Maxwell relations; thermodynamic equation of

state.

and integrated form of rate expressions up to second-order reactions, experimental methods of the

determination of rate laws, kinetics of complex reactions, opposing reactions parallel reactions and

consecutive reactions and their differential rate equations (steady-state approximation in reaction

mechanisms), chain reactions. Temperature dependence of reaction rates, Arrhenius equation,

activation energy. Collision theory of reaction rates, Lindemann mechanism, Physical adsorption,

chemisorption, adsorption isotherms. nature of the adsorbed state. Types of catalyst, specificity and

selectivity, mechanisms of catalyzed reactions at solid surfaces; effect of particle size and efficiency

of nanoparticles as catalysts. Enzyme catalysis, Michaelis-Menten mechanism, acid-base catalysis.

electrolytes. Molar conductivity at infinite dilution. Kohlrausch law of independent migration of ions.

Debye-Hückel-Onsager equation, Wien effect, Debye-Falkenhagen effect, Walden’s rules. Ionic

velocities, mobilities and their determinations, transference numbers and their relation to ionic

mobilities, determination of transference numbers using Hittorf and Moving Boundary methods.

Applications of conductance measurement: Quantitative aspects of Faraday’s laws of electrolysis,

rules of oxidation/reduction of ions based on half-cell potentials, applications of electrolysis in

metallurgy and industry. Chemical cells, reversible and irreversible cells with examples.

The electromotive force of a cell and its measurement, Nernst equation; Standard electrode (reduction)

potential and its application to different kinds of half-cells. Application of EMF measurements in

determining free energy, enthalpy and entropy of a cell reaction, equilibrium constants, and pH

values, using hydrogen, quinone-hydroquinone and glass electrodes. Concentration cells with and

without transference, liquid junction potential; determination of activity coefficients and transference

numbers. potentiometric titrations (acid-base, redox, precipitation).

determination of bond lengths of diatomic and linear triatomic molecules, isotopic substitution

Vibrational spectroscopy: Classical equation of vibration, computation of force constant, the amplitude of

diatomic molecular vibrations, anharmonicity, Morse potential, dissociation energies, fundamental

frequencies, overtones, hot bands, degrees of freedom for polyatomic molecules, modes of vibration,

the concept of group frequencies. Vibration-rotation spectroscopy: diatomic vibrating rotator, P, Q, R

branches. Raman spectroscopy: Qualitative treatment of Rotational Raman effect; Effect of nuclear

spin, Vibrational Raman spectra, Stokes and anti-Stokes lines; their intensity difference, rule of

mutual exclusion. Electronic spectroscopy: Franck-Condon principle, electronic transitions, singlet

and triplet states, fluorescence and phosphorescence, dissociation and predissociation. Nuclear

Magnetic Resonance (NMR) spectroscopy: Principles of NMR spectroscopy, Larmor precession,

chemical shift and low-resolution spectra, different scales, spin-spin coupling and high-resolution

spectra, interpretation of PMR spectra of organic molecules. Electron Spin Resonance (ESR)

spectroscopy: principle, hyperfine structure, ESR of simple radicals.