Syllabus (CHEMISTRY)

Course Type: MAJ-3

Semester: 3

Course Code: BCEMMAJ03C

Course Title: Physical Chemistry – I

(L-P-Tu): 4-2-0

Credit: 6

Practical/Theory: Combined

Course Objective: Course Objective of Major-3: The syllabus of Major-3 has been designed to provide the students with in-depth ideas on two of the most important aspects of Physical Chemistry: Chemical Thermodynamics and Chemical Kinetics. The three major modules consistin

Learning Outcome: Course Outcomes of Major-3: CO- 3.1: Introduce the basic definitions of Thermodynamics and the concepts of heat, energy, work, and their interrelationship. CO- 3.2: To understand the details of two major Thermodynamic Laws along with their applicability

THEORY:

THERMODYNAMICS –I (12L)

1. Zeroth and 1st law of Thermodynamics: Intensive and extensive variables; state and path functions; isolated, closed and open systems; zeroth law of thermodynamics; Concept of heat, work, internal energy and statement of first law; enthalpy, H; relation between heat capacities, calculations of q, w, U and H for reversible, irreversible and free expansion of gases (ideal and vander Waals) under isothermal and adiabatic conditions; Joule’s experiment and its consequence.

2. Thermochemistry: Standard states; Heats of reaction; enthalpy of formation of molecules and ions and enthalpy of combustion and its applications; Laws of thermochemistry; bond energy, bond dissociation energy and resonance energy from thermochemical data, Kirchhoff’s equations and effect of pressure on enthalpy of reactions; Adiabatic flame temperature; explosion temperature.

THERMODYNAMICS –II (30 L)

1. Second Law: Need for a Second law; statement of the second law of thermodynamics; Concept of heat reservoirs and heat engines; Carnot cycle; Physical concept of Entropy; Carnot engine and refrigerator; Kelvin – Planck and Clausius statements and equivalence of the two statements with entropic formulation; Carnot's theorem; Values of dQ/T and Clausius inequality; Entropy change of systems and surroundings for various processes and transformations; Entropy and unavailable work; Auxiliary state functions (G and A) and their variation with T, P and V. Criteria for spontaneity and equilibrium.

2. Thermodynamic relations: Maxwell's relations; Gibbs- Helmholtz equation, Joule-Thomson experiment and its consequences; inversion temperature; Joule-Thomson coefficient for a vander Waals gas; General heat capacity relations.

3. Partial properties and Chemical potential: Chemical potential and activity, partial molar quantities, relation between Chemical potential and Gibb's free energy and other thermodynamic state functions; variation of Chemical potential (μ) with temperature and pressure; Gibbs-Duhem equation; fugacity and fugacity coefficient; Variation of thermodynamic functions for systems with variable composition; Equations of states for these systems, Change in G,S H and V during mixing for binary solutions.

4. Chemical Equilibrium: Thermodynamic conditions for equilibrium, degree of advancement; van't Hoff's reaction isotherm (deduction from chemical potential); Variation of free energy with degree of advancement; Equilibrium constant and standard Gibbs free energy change; Definitions of KP, KC and KX; van't Hoff's reaction isobar and isochore from different standard states; Shifting of equilibrium due to change in external parameters e.g. temperature and pressure; variation of equilibrium constant with addition to inert gas; Le-Chatelier's principle and its derivation.

5. Dissociation of weak electrolyte. Solubility equilibrium.

6. Nernst’s distribution law; Application- (finding out Keq using Nernst distribution lawfor KI+I2 = KI3 and dimerization of benzene.

CHEMICAL KINETICS: (18 L)

Rate law, order and molecularity: Introduction of rate law, Extent of reaction; rate constants, order; Forms of rates of First, second and nth order reactions; Pseudo first order reactions (example using acid catalyzed hydrolysis of methyl acetate); Determination of order of a reaction by half-life and differential method; Opposing reactions, consecutive reactions and parallel reactions (with explanation of kinetic and thermodynamic control of products; all steps of first order).

READING REFERENCES:

1. Atkins, P. W. & Paula, J. de Atkins’ Physical Chemistry, Oxford University Press
2. Castellan, G. W. Physical Chemistry, Narosa
3. McQuarrie, D. A. & Simons, J. D. Physical Chemistry: A Molecular Approach, Viva Press
4. Levine, I. N. Physical Chemistry, Tata McGraw-Hill
5. Laidler, K. J. Chemical Kinetics, Pearson
6. Glasstone, S. & Lewis, G.N. Elements of Physical Chemistry
7. Rakshit, P.C., Physical Chemistry Sarat Book House
8. Rastogi, R. P. & Misra, R.R. An Introduction to Chemical Thermodynamics, Vikas
9. Bera, N. K., Ghosh, S., Ghosh, P., Vol-II& III, Physical Chemistry Concepts & Models, Techno World, Kolkata
10. Ashish Kumar Nag, Physical Chemistry (Vol-I & II), McGraw Hill Education (India) Pvt. Ltd.

11. K. L. Kapoor, A Textbook of Physical Chemistry, Vol-I to Vol-V, Macmillan Publishers India Ltd. 2004.

12. Ghoshal, A. Numerical Problems on Physical Chemistry, Books & Allied Pvt. Ltd. Kolkata.

PRACTICALS:

1. Determination of heat of neutralization of a strong acid by a strong base.
2. Study of kinetics of acid-catalyzed hydrolysis of methyl acetate.
3. Study of kinetics of decomposition of H2O2by FeCl₃ and Neutral KI method.
4. Determination of partition coefficient for the distribution of I2 between waterand CHCl₃.

REFERENCES FOR PRACTICALS:

1. University Hand Book of Undergraduate Chemistry Experiments, edited by Mukherjee, G N., University of Calcutta.
2. Levitt, B. P. edited Findlay’s Practical Physical Chemistry Longman Group Ltd.
3. Gurtu, J. N., Kapoor, R., Advanced Experimental Chemistry S. Chand & Co. Ltd.
4. Saharay, S. K. &Basu, A. S. A Guide to Practical Physical Chemistry, University of Burdwan.

5. Concise Practical Chemistry, Karmakar, P., Sarkar(Sain), R., Ray, S., Ghosh, A. K., The New Book Stall, Kolkata