Kinetics, Electrochemistry, with Basic Laboratory Course in Physical Chemistry
Kinetics
Basics: Formal Kinetics, reaction rates and differential equations; integrative and differential methods, reaction orders; Reaction laws for 1st and 2nd order and comparison 0 to 3rd order; coupled reactions: parallel, sequence and back reactions, with examples from photophysics; kinetics of complex reactions: quasistationary state (Bodenstein principle), chain reactions, explosions, catalysis, autocatalysis; temperature dependence (Arrhenius and Eyring theories); further dependences: pressure, polarity (Bell-Evans-Polanyi principle), ionicity, substituent effects (Hammett equation), isotope effects; applicational aspects: photochemical kinetics, biokinetics, oscillating reactions
K. H. Laidler, "Chemical Kinetics", 3rd edition, Harper-Collins,
1987.
P.W. Atkins: "Physical Chemistry", Oxford University Press, chapters
28, 29, 30
Electrochemistry
Basics: electrolytes, ionic conduction, electrolysis, galvanic element, Faraday´s laws, systems of units (MKSA vs cgs). Electrolytic conduction: (specific) resistance and (specific) conductivity, molar and equivalent conductivity. Kohlrausch´s law and limiting equivalent conductivity, ion mobility, microscopic explanation. Hüttorf transport number. Hydration of ions. Electrode potentials: electrical, electrochemical, Galvani-, Volta-Potentials, EMF. Nernst´s equations for metal, redox, gas electrodes. Reference electrodes, NHE, standard potential, electromotive series. Thermodynamics of EMF. Electrodes of second kind. Debye-Hückel theory: Concept of ionic cloud, charge distribution and el. potential (Poisson-equ.), Laplacian in polar coordinates and simplification to central potential. Ansatz for potential(r) as screened Coulombic potential, determination of radius for ionic cloud, normalisation. Debye-Onsager equ. for conductivity of dilute electrolytes. Influence of ac fields. Activity: mean activity coefficient, its concentration dependence. Weak electrolytes: Ostwald´s dilution law, dissociation field effect. pH: concept, buffer. Diffusion potential: origin and calculation, concentration series, elimination of diffusion potential. Electrolysis: Helmholtz double layer, electrode processes: kathodic and anodic current, Butler-Volmer-equation for the current as f(electrode polarisation), deviations due to concentration changes or diffusion. Tafel equ.
P.W. Atkins:
"Physical Chemistry", Oxford University Press, chapters 11,12,
32;
C. H. Hamann, W. Vielstich: "Elektrochemie I, II": Verlag Chemie,
Taschentext Vol. 41 & 42, 1985.