UNIVERSITY OF MADRAS
B.Sc. DEGREE COURSE IN CHEMISTRY
SEMESTER SYSTEM WITH CREDITS
(Effective from the Academic Year 2003-2004)

Semester IV - Paper IV - General Chemistry IV

Duration: 3 hrs
Maximum Marks: 100
Credits: 4

Unit - I

1.1 Nitrogen family

Comparative study of N, P. As, Sb and Bi - elements, oxides, oxyacids, halides and hydrides valeney states - preparation, properties, structure and uses of hydrazine, hydroxylarnine and hydrazoic acids, preparation and uses of NaBiO₃.

1.2 Oxygen family

Comparative study of O, S, Se and Te - elements, hydrides, oxides and oxyacids of sulphur including peroxy acids and thionic acids

1.3 Halogens

Comparative study of F, Cl, Br, I and At -- elements reactivities, hydracids, oxides and oxyacids, inter halogen compounds, pseudo halogens and positive iodine. Flourides of oxygen. Exceptional properties of Fluorine, classification of halides.

1.4 Noble Gases

Electronic configuration and position in the periodic table. Applications, clatharates and compounds of xenon, hybridization and geometries of XeF₂, XeF₄,, XeF₆, XeOF₄.

Unit - II

2.1 Elimination Reactions:

Hoffmann and Sayetzeffs rules cis and trans eliminations -mechanisms of E1 and E2 reactions. Elimination Vs substitution. Re-activities of methyl, ethyl, propyl, isoprophy, n-butyl, allyl, vinyl and benzyl and intermediate complex mechanism - effect of substituents on reactivity.

2.2 Alcohol's and Phenols:

Synthesis bty Grignard method and oxy metcuration - chemical reactivity. Polyhydric alcohols - clevage reactions with periodic acid, lead tetractetate, osmium tera oxide. Unsaturated alcohols - preparation and reactions of allyl alcohol.

2.3 Phenols:

Acidic character of phenols - explanation on the basis of resonance stabilization. Ring substitution in phenol - orientation of phenolic group towards electrophiles. mechanisms of esterification, nitration, suiphonation, halogenation coupling with diazomum salts. Kolbe's reaction, Reimer-Tiemarin reaction, Gattermann, Lederer, Manasse and Houben - Hoesh reactions. Cresols, nitrophenols, aminophenols, di and tn hydric phenols alpha and beta nathols - preparation and properties.

Unit - III

3.1 Third law of Thermodynamics:

Nernst heat theorem statement of Third law of thermodynamics. Evaluation and absolute entropy from heat capacity measurements. Exception to Third law.

3.2 Partial Molar Properties:

Chemical potential - Gibbs Duhem equation - effect of temperature and pressure on chemical potential - chemical potential in system of ideal gases - Duhem - Margules equation.

3.3 Thermodynamic

Derivation of the law of chemical equilibrium - reaction isotherm - standard free energy change - standard free energy change and equilibrium constant - variation of equilibrium constant with temperature - Vant Hoff isochore.

3.4 Concept of fugacity and activity

Determination of fugacity of gas - activity and activity coefficient.