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Physical Chemistry I (CHM 55) Syllabus

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:

"Physical Chemistry", 5th Edition, McGraw Hill Higher Education,

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


Student Solutions Manual (ISBN: 0-07-239360-2).

Physical Chemistry Labs (CHM 55L)

Laboratory courses will illustrate the lecture topics and will introduce students to methods
and reasoning of physical chemistry experiment.

1. Zeroth Law of Thermodynamics

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

2. The First Law of Thermodynamics

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


3. The Second and Third Laws of Thermodynamics

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

Physical Chemistry I


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.



Introduction to Safety Rules and Safety Behavior in the Lab.

Exp.# 1:

The BestLeastSquareFit (Theoretical Enclosure).

Exp.# 2:

Determination of Molar Mass of Volatile Liquid by Dumas Method.

Part A. Molar Mass of Carbon Tetrachloride.

Exp.# 3:

Determination of Molar Mass of Volatile Liquid by Dumas Method.

Part B. Molar Mass of an Unknown.

Exp.# 4:

Degree of Association of Acetic Acid Vapor by Dumas Method.

Exp.# 5:

Temperature Dependence of Densities of Liquids.

Part A. Calibration of Pycnometers at Series of Temperatures.

Exp.# 6:

Temperature Dependence of Densities of Liquids.

Part B. Liquid Density measurements at Series of Temperatures.

Exp.# 7:

The Viscosity of Liquids. Part A. Calibration of Viscometers by Water.

Exp.# 8:

The Viscosity of Liquids. Part B. Viscosity of an Unknown.

Exp.# 9:

Conformation of Macromolecules by DiluteSolution Viscometry.


Calorimetry. The Enthalpy of Neutralization.