Chemical Energetics and Radiochemistry - रासायनिक ऊर्जाविज्ञान एवं रेडियो रसायनिकी

Program/Class:

Degree/ Bachelor of

Science

Year: Third

Semester: Sixth

Subject: Chemistry

Course Title: Chemical Energetics and Radio Chemistry

Course Learning Outcomes

Upon successful completion of this course students should be able to describe laws of thermodynamics and its applications, phase equilibria of one and two component system, electro chemistry ,ionic equilibrium applications of conductivity and potentiometric measurements

Credits: 4

Core Compulsory

Max. Marks: –25+75

Min. Passing Marks: 40

Unit

Topics

I

Thermodynamics-1 :

First Law of Thermodynamics : Statement , definition of internal energy and enthalpy. Heat capacity ,heat capacities at constant volume and pressure and their relationship. Joule’s law – Joule Thomson coefficient and inversion temperature . Calculation of w, q, dU & dH for the expansion of ideal gases under isothermal and adiabatic conditions for reversible process. Thermochemistry: Standard state, standard enthalpy of formation – Hess’s law of heat summation and its applications. Heat of reaction at constant pressure and at constant volume . Enthalpy of neutralization . Bond dissociation energy and its calculation from thermo-chemical data , temperature dependence of enthalpy. Kirchhoff’s equation

II

Thermodynamics II

Second Law of Thermodynamics, Need for the law, different statements of the law, Carnot cycle and its efficiency. Carnot theorem. Thermodynamic scale of temperature. 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 change, Clausius inequality , entropy as a criteria of spontaneity and equilibrium. Entropy change in ideal gases and mixing of gases. Gibbs and Helmholtz Functions Gibbs function (G) and Helmhotz function (A) as thermodynamic quantities. A & G as criteria for thermodynamic equilibrium and spontaneity, their advantage over entropy change, Variation of G and A with P, V and T. Third Law of Thermodynamics ; Nernst heat theorem , statement and concept of residual entropy.Nernst distribution law – Thermodynamic derivation, applications .

III

Electrochemistry: Electrical transport:- Conduction in metals and in electrolyte solutions, specific conductance molar and equivalent conductance, measurement of equivalent conductance, variation of molar, equivalent and specific conductances with dilution. Migration of ions and Kohlrausch law , Arrhenius theory of electrolyte dissociation and its limitations. Weak and strong electrolytes . Ostwald’s dilution law, its uses and limitations . Debye-Huckel-Onsager equation for strong electrolytes (elementary treatment only) . Transport number, definition and  etermination by Hittorf method and moving boundary method.

IV

Ionic Equilibrium: Electrode reactions, Nernst equation, derivation of cell EMF and single electrode potential, standard hydrogen electrode-reference electrodes and their applications, standard electrode potential, sign conventions, Electrolytic and Galvanic cells–Reversible and irreversible cells, conventional representation of electrochemical cells. EMF of a cell and its measurement. Definition of pH and pKa , determination of pH using hydrogen, quinhydrone and glass electrodes by potentiometric methods. Buffers – Mechanism of buffer action, Henderson-Hazel equation, application of buffer solution. Hydrolysis of salts

V

Photo Chemistry: Interaction of radiation with matter, difference between thermal and photochemical processes . Laws of photochemistry: Grothus- Drapper law, Stark-Einstein law, Jablonski diagram depicting various processes occurring in the excited state, qualitative description of fluorescence, phosphorescence, non-radiative processes (internal conversion, intersystem crossing), quantum yield, photosensitized reactions – energy transfer processes (simple examples), kinetics of photochemical reaction.

VI

Colligative Properties-Ideal and non-ideal solutions, methods of expressing concentrations of solutions, activity and activity coefficient. Dilute solution, colligative properties, Raoult’s law, relative lowering of vapour pressure, molecular weight determination, Osmosis, law of osmotic pressure and its measurement, determination of molecular weight from osmotic pressure, Elevation of boiling point and depression of freezing, Thermodynamic derivation of relation between molecular weight and elevation in boiling point and depression in freezing point. Experimental methods for determining various colligative properties. Abnormal molar mass, Van’t Hoff factor, Colligative properties of degree of dissociation and association of solutes

VII

Surface Chemistry

Adsorption: Physical and chemical adsorption; Freundlich and Langmuir adsorption isotherms; multilayer adsorption and BET isotherm (no derivation required); Gibbs adsorption isotherm and surface excess; Heterogenous catalysis (single reactant); Colloids:Lyophobic and lyophilic sols, Origin of charge and stability of lyophobic colloids,Coagulation and Schultz-Hardy rule, Zeta potential and Stern double layer (qualitative idea), Tyndall effect; Electrokinetic phenomena (qualitative idea only); Stability of colloids and zeta potential; Micelle formation

VIII

Radiochemistry

Natural and induced radioactivity; radioactive decay-a-decay, b-decay, g-decay; neutrom emission, positrom emission, electron capture; unit of radioactivity (Curie); half life period; Geiger-Nuttal rule, radioactive displacement law, radioactive series. Measurement of radioactivity: ionization chamber, Geiger counters, scintillation counters. Applications: energy tapping, dating of objects, neutron activation analysis, isotopic labelling studies, nuclear medicine-99mTc radiopharmaceuticals