Semester II

CHEMICAL ENERGETICS, EQUILIBRIA & FUNCTIONAL ORGANIC CHEMISTRY

(Credits: Theory-04, Practicals-02) Theory: 60 Lectures

Section A Physical Chemistry-1 (30 Lectures)

UNIT - I

Chemical Thermodynamics, Energetics and Chemical Equilibrium: (18 Lectures)

Part - A

Review of thermodynamics (scope,limitations). Laws of thermodynamics- First law and second

law (statements only). Definition of thermochemistry, Enthalpy,internal energy,Enthalpy of formation or
heat of formation, standard enthalpies of formation, combustion, neutralisation and dilution. Hess law
of constant heat summation and its applications- calculation of enthalpies of formation, enthalpy
changes in slow reactions, bond energies. Variation of enthalpy and internal energy of a reaction with
temperature – derivation of Kirchhoff’s equation.

Part – B

Statement of Third Law of thermodynamics. Gibb’s free energy (ΔG), Standard free energy change
(ΔG0). Thermodynamic derivation of the law of chemical equilibrium( law of mass action). Distinction
between ΔG and ΔGo . Relationships between Kp, Kc and Kx for reactions involving ideal gases, Le
Chatelier’s principle, Application of Lechatlier’s principle to Pcl5 decomposition,Haber’s process, contact
process.

UNIT - II

Ionic Equilibria: (12 Lectures)

Part- A

Degree of ionization-Strong, moderate and weak electrolytes, ionization constant, ionic product of
water. Ionization of weak acids and bases-pH scale, problems. Salt hydrolysis-calculation of hydrolysis
constant, degree of hydrolysis and pH for different salts. Buffer solutions- Buffer action of acidic buffer (
acetic acid + Sodium acetate) and basic buffer ( ammonium hydroxide + ammonium chloride),
Henderson’s equation ( no derivation).

Part - B

Common ion effect, Solubility and solubility product of sparingly soluble salts – any five applications of
solubility product – Salting out of soap, purification of common salt, applications in qualitative and
quantitative analysis.
 Section -B
Organic Chemistry (30 Lectures)

UNIT - III
Part A
Aromatic hydrocarbons
Preparation of Benzene: From phenol, by decarboxylation, from acetylene, from benzene sulphonic
acid. Electrophilic substitution reactions: Nitration, Chlorination, Friedel-Craft’s alkylation and acylation
of Benzene with mechanisms,Sulphonation(Mechanism not required), Side chain oxidation of alkyl
benzenes (upto 3 carbons on benzene). (Mechanism not required)
Part B

Alkyl and Aryl Halides

Alkyl Halides: Preparations: from alkenes and alcohols. Reactions: hydrolysis (SN1, SN2 and SNi)
reactions with mechanism, nitrite & nitro formation, nitrile & isonitrile formation. Aryl Halides:
Preparation: Chloro, bromo by Sandmeyer & Gattermann reactions and iodo-benzene from Benzene
diazonium chloride. Reactions of Chlorobenzene: replacement by –OH group and effect of nitro
substituents. Benzyne Mechanism: KNH2/NH3. Reactivity and Relative strength of C-Halogen bond in
alkyl, allyl, benzyl, vinyl and aryl halides.

UNIT - IV
Part A
Alcohols and Ethers
Alcohols: Preparation: Preparation of 1о , 2о and 3о alcohols using Grignard reagent, Ester hydrolysis,
Reduction of aldehydes, ketones, carboxylic acids. Reactions: With sodium, Lucas test, esterification
with mechanism, oxidation (with PCC, alk. KMnO4. Oppeneauer oxidation Diols: oxidation of diols with
HIO4 and Lead tetraacetate. Pinacol-Pinacolone rearrangement. Ethers (aliphatic and aromatic):
Preparation of Ether (Diethyl ether) by Williamson’s synthesis: Cleavage of ethers with HI in both the
conditions.

Part B
Phenols: Preparation from Cumene, from diazonium salts. Reactions: Nitration, Bromination and
sulphonation. ReimerTiemann Reaction with mechanism, Gattermann-Koch Reaction, Kolbes’s reaction.

UNIT - V
Part A Aldehydes and ketones

Preparations: from acid chlorides and from nitriles. Reactions (only reactions) (with respect to
Acetaldehyde, acetone) – Reaction with HCN, NaHSO3, NH2-G derivatives, Iodoform test. Wittig reaction
and Clemensen reduction and Wolff Kishner reduction. Meerwein-Pondorff Verley reduction
Part B

Mechanisms of Aldol Condensation (Acetaldehyde), Cannizzaro’s reaction (Formaldehyde), Benzoin

condensation (Benzaldehyde) only.