FALL SEMESTER

COURSE: 09176 ADVANCES IN PHYSICAL CHEMISTRY

INSTRUCTOR: PROF. DR. OĞUZ OKAY

TIME: TUESDAY 14.00-17.00

PLACE: PHYSICAL CHEMISTRY LIBRARY

CONTENT:

WEEK	TOPICS
1.	CHEMICAL THERMODYNAMICS: Definitions, units, ideal behavior of gases, deviations from ideal behavior (excluded volume effect and intermolecular interactions), derivations of the van der Waals and Virial equations, Boyle temperature of gases versus Theta temperature of polymers, CALCULUS: derivatives, training using the ideal gas equation, thermal expansion coefficient, isothermal compressibility, total differential, state functions
2.	PV Isotherm of real gases, phase transitions, calculation of the critical point, Corresponding states, examples. LAWS OF THERMODYNAMICS: work and heat, reversible and irreversible processes, 1st Law and internal energy, enthalpy, Cp, Cv, internal pressure versus solubility parameters, Joule and Joule-Thomson experiments, internal energy changes during processes involving ideal gases.
3.	Spontaneous processes and their direction, converting heat into useful work, 2nd Law, thermodynamic efficiency and Carnot cycle. Entropy and its changes during various processes including the Joule experiment and mixing processes, Boltzman equation, entropy changes in the system, surroundings and in the universe.
4.	Examples using the 1st and 2nd Laws of Thermodynamics, refrigerator and heat pump. Gibbs free energy, Helmholtz free energy, Gibbs equations, Maxwell relations, calculation of the changes of the state functions U, H, S, G, and A during real processes. Derivation of the ideal gas law using statistical thermodynamics. Examples.
5.	A CASE STUDY: Thermodynamic analysis of the deformation of rubber, internal energy, enthalpy, entropy, Gibbs and Helmholtz free energy changes during deformation, their calculations using the thermomechanical data. STATISTICS: statistical probability, Kerrich experiment, the two laws of probability, examples in addition and chain polymerizations, random variables, probability function, averages, Binomial distribution, Poisson distribution, Exponential distribution, Gaussian distribution, Molecular weight averages of polymers. STATISTICAL AND KINETIC THEORIES: calculations of moments and average molecular weights in condensation and addition polymerizations, application of statistical methods in crosslinked systems.
6.	CONFIGURATION OF A POLYMER CHAIN: parameters determining the chain configuration, random coil, end-to-end distance and radius of gyration, statistical distribution of end-to-end distances, random walk model, probability function of the end-to-end distance for a freely-jointed chain, average values of the end-to-end distances of chains, deviations in real chains, Theta condition and unperturbed dimensions of polymers.
7.	STATISTICAL THEORY OF RUBBER ELASTICITY: elasticity of chain molecules, entropy of a single chain, work done on a chain during its deformation, force versus deformation of single chains, elasticity of a molecular network, extension ratios, entropy change and work during deformation, elastic modulus, true and nominal stresses. Elastic properties of swollen rubber, elastic modulus of swollen rubber.
8.	MIDTERM EXAM
9.	SOLUTION OF MIDTERM QUESTIONS AND REVIEW OF THE TOPICS COVERED
10.	MIXING PROCESSES AND SOLUTIONS: open systems, chemical potential, phase and reaction equilibria, their predictions using the chemical potentials, chemical potential of pure gases, gas mixtures, ideal solutions, ideal solutions versus ideal gases
11.	İdeal and real solutions, entropy, enthalpy, Gibbs free energy of mixing, osmotic pressure, colligative properties and methods for molecular weight determination. POLYMER SOLUTION THERMODYNAMICS: definition of segment, Flory-Huggins lattice theory, mixing of polymer chains with solvent molecules in a lattice, entropy, enthalpy changes during mixing, Chi parameter, Gibbs free energy of mixing.
12.	Chemical potentials of solvent and polymer in solutions, phase equilibria, phase separation SWELLING: Energy changes during the swelling process, derivation of the Flory-rehner equation.

TEXT BOOKS: IN LEVINE: PHYSICAL CHEMISTRY

PJ FLORY: PRINCIPLES OF POLYMER CHEMISTRY

Weight of the Course Work:

Mid-Term: 40%

Final: 60%

Attendance is Mandatory