CHEMICAL ENERGETICS, EQUILIBRIA & FUNCTIONAL ORGANIC CHEMISTRY

Review of thermodynamics and the first law of thermodynamics.

Joule-Thomson effect, Joule-Thomson coefficient for an ideal gas & real gas, inversion temperature. Important principles and definitions of thermochemistry. Concept of standard state and standard enthalpies of formations, integral and differential enthalpies of solution and dilution.

Calculation of bond energy, bond dissociation energy and resonance energy from thermochemical data. Variation of enthalpy of a reaction with temperature – Kirchhoff’s equation. Second and third law of thermodynamics, concept of entropy- entropy as a state function, entropy as a function of V & T, entropy as a function of P & T, entropy change in physical processes and calculation of absolute entropies of substances.

Chemical Equilibrium: Free energy change in a chemical reaction, thermodynamic derivation of the law of chemical equilibrium. Distinction between ΔG and ΔG^o, Le Chatelier’s principle. Relationships between Kp, Kc and Kx for reactions involving ideal gases.

Ionic Equilibria: Strong, moderate and weak electrolytes, degree of ionization, factors affecting degree of ionization, ionization constant and ionic product of water. Ionization of weak acids and bases, pH scale, common ion effect. Salt hydrolysis-calculation of hydrolysis constant, degree of hydrolysis and pH for different salts, buffer solutions. Solubility and solubility product of sparingly soluble salts – applications of solubility product principle.

Aromatic hydrocarbons: Aromaticity- Benzenoids and Hückel’s rule. Preparation (Benzene): from phenol, by decarboxylation, from acetylene, from benzene sulphonic acid.

Reactions (Benzene)- Electrophilic substitution, nitration, halogenation and sulphonation. Friedel-Craft’s reaction (alkylation and acylation) (upto 4 carbons on benzene). Side chain oxidation of alkyl benzenes (upto 4 carbons on benzene).

Alkyl Halides (Upto 5 Carbons): Types of nucleophilic substitution (S_N1, S_N2 and S_Ni) reactions and elimination reactions (E1, E2 and E1cB). Elimination vs  substitution.

Preparation from alkenes and alcohols.

Reactions- hydrolysis, nitrite & nitro formation, nitrile & isonitrile formation. Williamson’s ether synthesis.

Aryl Halides: Preparation from Phenol, Sandmeyer & Gattermann reactions.

Reactions (Chlorobenzene): Aromatic nucleophilic substitution (replacement by –OH group) and effect of nitro substituent. Benzyne Mechanism: KNH₂/NH₃ (or NaNH₂/NH₃). Reactivity and relative strength of C-Halogen bond in alkyl, allyl, benzyl, vinyl and aryl halides.

Alcohols: Preparation of 1^о, 2^о and 3^о alcohols using Grignard reagent, ester hydrolysis, reduction of aldehydes, ketones, carboxylic acid and esters.

Reactions with sodium, HX (Lucas test), esterification, oxidation (with PCC, alk. KMnO₄, acidic dichromate, conc. HNO₃). Oppeneauer oxidation diols, oxidation of diols. Pinacol-Pinacolone rearrangement.

Phenols (Phenol only): Preparation- Cumene hydroperoxide method, from diazonium salts.

Reactions: Electrophilic substitution- Nitration, halogenation and sulphonation. Reimer-Tiemann Reaction, Gattermann-Koch Reaction, Houben–Hoesch Condensation, Schotten – Baumann Reaction.

Ethers (aliphatic and aromatic): Cleavage of ethers with HI.

Reactions – Comaparative reactivity of formaldehye, acetaldehyde, acetone and benzaldehyde, acid and base catalyzed mechanism of nucleophilic addition reaction, reaction with HCN, ROH, NaHSO₃, NH₂-G derivatives. Iodoform test. Aldol Condensation, Cannizzaro’s reaction, Wittig reaction, Benzoin condensation. Clemmensen reduction, Wolff Kishner reduction and Meerwein-Pondorff Verley reduction.