Download Undergraduate physical chemistry final examination topics 1

Undergraduate physical chemistry final examination topics
1. Specification of a thermodynamic system. Postulates (axioms) of thermodynamics.
Entropy, energy, work and heat. Equilibrium in isolated and isentropic systems. Laws of
classical thermodynamics.
2. Entropy- and energy-based fundamental equations. Equations of state. Energy- and
entropy-based intensive variables. Equilibrium in isobaric, isothermal and isobaricisothermal systems. Equilibrium conditions in terms of intensive and extensive quantities.
3. Mathematical formalism of thermodynamics. Fundamental equations for the functions S,
U, H, F and G; derivatives of the relevant functions. Euler formula, Gibbs-Duhem
equation, Maxwell relations, Gibbs-Helmholtz equation.
4. Basic principles of statistical thermodynamics. Probability distribution function of the
energy and partition function on microcanonical and canonical ensembles. Calculation of
canonical partition function using molecular contributions. Calculation of thermodynamic
quantities (S, U, H and F) from partition functions.
5. Phase equilibria. Gibbs phase rule and its application. Phase stability and phase
diagrams of pure components. Equilibrium and phase diagrams of binary systems.
Equilibrium and phase diagrams of multicomponent systems. Construction of phase
diagrams from experimental data. Separation of components based on phase diagrams.
6. Ideal and real mixtures. Fugacity, activity and related standard quantities. Colligative
properties (freezing point depression, boiling point elevation, vapour pressure depression,
osmosis); characterisation of related equilibria.
7. Chemical equilibrium in reactive systems. Equilibrium constant and related standard
quantities of reactions. Temperature- and pressure dependence of the equilibrium
constant. Calculation of the equilibrium constant on a canonical ensemble.
8. Transport phenomena. The general linear transport equation and its application for
diffusion and viscous flow. Transport phenomena in electrolyte solutions (diffusion,
diffusion potential, electric conduction).
9. Collision theory of chemical reactions. Transition state theory for bimolecular and
unimolecular reactions. General mass-action equations for elementary reactions, their
solution. Experimental determination of the order of reaction. Temperature and pressure
dependence of the reaction rate constant.
10. Reaction mechanisms. Methods to solve the system of kinetic equations for composite
reactions. Steady-state approximation and its applicability. Chain reactions.
11. Catalysis and inhibition. Autocatalysis, autoinhibition and their detection based on the
change of reaction order. Acid-base catalysis. Kinetics of heterogeneous reactions;
heterogeneous catalysis.
12. Detectors, sensors and measuring devices. Control and regulation. Data collection and
regulation using computers.
13. Application of different optical methods to study equilibria and kinetics of chemical
reactions.
14. Thermodynamics of systems containing electrically charged particles (electroneutrality
principle, electrochemical potential, mean activity of ions, Born formula of solvation,
Debye-Hückel limiting law). Thermodynamic description of galvanic cells.
Characterisation and classification of electrodes.
15. Electrochemical power sources, electrolysis. Electrochemical corrosion and corrosion
protection.
16. Application of different electrochemical methods to study thermodynamic equilibria and
kinetics of chemical reactions.
17. Basic principles of quantum mechanics: physical quantities, their measurement, state
functions, expectation values. The Schrödinger equation. Stationary states, simultaneous
measurement of physical quantities, the Heisenberg uncertainty principle.
18. Quantum mechanical description of a hydrogen atom: solving the stationary Schrödinger
equation (calculating energies and eigenfunctions); degeneration, visualisation of orbitals
and electron densities. The spin of the electron.
19. Quantum mechanical description of multielectron systems: Hamiltonian, stationary
Schrödinger equation, independent electron model (IEM), Pauli principle, Slater
determinant. Electronic structure of multielectron systems: orbitals, energy of orbitals,
Aufbau principle, electron configuration. Characterisation of atomic states and their
notation. Hund’s rules.
20. Electronic structure of molecules, their Hamiltonian. The orbitals of H + ion. LCAO-MO
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approximation. Structure of the H2 molecule using VB and MO model. Electronic structure
of general diatomic molecules. Electronic structure of the water molecule using VB and
MO model: canonical and localised orbitals; hybrid orbitals.
Theoretical background of chemical structure determination. Principles of spectroscopic
methods. Different methods depending on energy, on the molecular modes. Interpretation
of simple spectra.
Rotational and vibrational spectroscopy. Description of a diatomic molecule as a rigid
rotor; energy levels and selection rules. Different types of spinning tops. Applications of
rotational spectroscopy. Classical and quantum mechanical description of a diatomic
molecule as a harmonic oscillator; energy levels and selection rules. Generalisation to
multiatomic molecules’ vibration. Internal coordinates and normal coordinates. Role of
symmetry. Applications in IR and Raman spectroscopy.
Electron spectroscopy: principles of UV and visible spectroscopy; selection rules,
vibrational fine structure. Practical applications: excitation decay phenomena,
fluorescence and phosphorescence. Principles of photoionisation spectroscopy; selection
rules. X-ray photoelectron spectroscopy (ESCA).
NMR and ESR spectroscopy. Quantum mechanical description of magnetic properties of
particles. Nuclear spin and the principle of NMR spectroscopy. Qualitative properties of
NMR spectra; chemical shift and spin-spin coupling. ESR spectroscopy and its practical
applications.
Excess surface energy and its thermodynamic consequences. Surface tension. Pressure
at curved interfaces. Equilibrium vapour pressure of droplets. Solubility of small solid
particles.
Thermodynamics of interfaces according to Gibbs. Gibbs adsorption equation and its
practical applications. Capillary active and capillary inactive substances. Adsorption
isotherms. Equation of state of an adsorbed surface layer.
Classical (DLVO) theory of colloid stability. Coagulation kinetics. Effect of the electrolyte
concentration on the rate of coagulation. Sedimentation, isothermal recrystallisation and
aggregation.
Association colloids and the formation of micelles. The hydrophobic interaction. Micelle
mixtures. Solubilisation; formation of polymer-surfactant complexes.
Macromolecular colloids; solutions of polymers. Random coil structure of polymer
molecules. Polymer gels and polyelectrolytes.
Basics of rheology. Deformation types and their explanation based on material structure.
Rubber elasticity.