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C. W. POST CAMPUS

This course is an introduction to chemical thermodynamics and chemical kinetics with

applications to gases, solutions and phase equilibria to provide a firm foundation for

understanding the physical principles that govern chemical and biological systems.

Experimental physical chemistry methods are emphasized.

Prerequisite: Chemistry 22 or 25, Chemistry 37, Physics 4, Mathematics 8.

Fall, four credits. Three hours lecture. Four hours laboratory.

Mandatory TEXT:

by Ira N. Levine, ISBN: 0-07-231808-2.

Recommended:

Laboratory courses will illustrate the lecture topics and will introduce students to methods

and reasoning of physical chemistry experiment.

LECTURE TOPICS CHM 55

A. Properties of gases. Equation of state. The ideal gas. Isothermal, isobaric and

isochorus processes. Mixtures of gases.

B. Kinetic-molecular theory of gases. Distribution of speeds. Diffusion and effusion.

Molecular collisions.

C. Real gases. Van der Waals approach. Virial coefficients. The liquefaction of

gases.

A. Work and heat. Internal energy. Conservation of energy. The First Law and its

universal applications.

B. System and surroundings. Exact and inexact differential. Heat capacities.

C. Isolated systems. Adiabatic versus isothermal processes.

D. First thermodynamic functions. Enthalpy and its calculations.

E. Thermodynamic relationships. Temperature, pressure, and volume variations of

enthalpy and internal energy. Isoenthalpic process, JouleThompson effect.

F. Chemical applications of the First Law. Thermochemistry. Standard quantities of

formation. The Hess' Law. Variation of reaction enthalpy with temperature.

Physical Chemistry I

Syllabus

A. Concept of spontaneity. Conversions of heat to work and vice versa. The law of

machinery. Carnot cycle. Thermodynamic formulation of absolute temperature.

Carnot, Clausius and Kelvin formulation of entropy. Reversibility. Criteria of

spontaneity and entropy increase in isolated systems.

B. Entropy is a state function. Calculations of entropy change. Isothermal change as

quasiisoentropic process and adiabatic change as true isoentropic process.

C. Entropy calculations for specific processes. Entropy and its standard reaction

quantity. Trouton's rule. Experimental determination of entropy.

D. The inattainability of absolute zero temperature. The Nernst heat theorem. The

Third Law.

E. Gibbs free energy and spontaneity. Reformulation of the Second Law in terms of

thermodynamic functions of the system. Maximum of non-expansion work.

Standard molar Gibbs free energies.

F. Unification of the First and Second Laws: the fundamental equation. The Maxwell

relations. Properties of Gibbs free energy: effects of pressure, volume and

temperature on Gibbs free energy change.

G. Chemical potential of a pure substance. Real gases: the fugacity. Standard

states of real gases. Fugacity versus pressure

H. Physical transformation of pure substances. Phase equilibrium.

I. Simple mixtures and partial molar quantities. Chemical potential and partial molar

Gibbs energies. The GibbsDuhem equation for the mixtures. Thermodynamics

of mixing. Chemical potential of liquids. Ideal and non-ideal solutions. The

common colligative properties. Activities. Activities in terms of molalities.

4. Chemical Equilibrium

A. Spontaneity of chemical reactions. Gibbs energy minimum. Perfect gas equilibria.

Gibbs free energy change for the reaction and chemical quotient. Expression for

thermodynamic equilibrium constant. Equilibrium Calculations. Response of

equilibrium to pressure, volume and temperature. The van't Hoff equation

B. Acid-base equilibrium and pH-scale in terms of activities. Acid-base titration.

Acid-base indicators. Buffers. HendersonHasselbach approximation useful in

biology applications

C. Biological activity: the thermodynamics of ATP. Biological standard states.

Anaerobic and aerobic metabolism. Glucose transformations. Myoglobin and

hemoglobin (briefly).

D. Solubility and complex formation equilibria

E. Equilibrium electrochemistry. Ion activities Electrochemical cells. Standard

potentials. The electrochemical series. The Nernst equation. Thermodynamic

functions from cell potential measurements. Solubility constants. pH and pK

measurements.

Physical Chemistry I

Syllabus

5. Molecules in Motion

A. Collisions with walls and surfaces. Transport properties of gases. The

thermodynamic view of diffusion.

B. Empirical chemical kinetics. Experimental techniques. The rates of reactions.

Integrated rate laws of simple reactions. Half-lives and rate constants.

Dependence of half-life on concentration.

Checkin:

Exp.# 1:

Exp.# 2:

Part A. Molar Mass of Carbon Tetrachloride.

Exp.# 3:

Part B. Molar Mass of an Unknown.

Exp.# 4:

Exp.# 5:

Part A. Calibration of Pycnometers at Series of Temperatures.

Exp.# 6:

Part B. Liquid Density measurements at Series of Temperatures.

Exp.# 7:

Exp.# 8:

Exp.# 9:

Exp.#10:

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