Thermodynamics, Fundamentals (First law of thermodynamics and equilibrium, Second law, variational statement of Second law, application: thermal equilibrium and temperature, auxiliary functions and Legendre transforms, Maxwell relations, extensive functions and the Gibbs-Duhem equation, intensive functions); Conditions for Equilibrium and Stability (multiphase equilibrium, stability, application to phase equilibria, plane interfaces); Statistical Mechanics (the statistical method and ensembles, microcanonical ensemble and the rational foundation of thermodynamics, canonical ensemble, generalized ensembles and the Gibbs entropy formula, fluctuations involving uncorrelated particles, alternative development of equilibrium distribution functions); Non-Interacting (Ideal) Systems (occupation numbers, photon gas, phonon gas or fluctuations of atomic positions in a cold solid, ideal gases of real particles, electrons in metals, classical ideal gases, the classical limit, thermodynamics of an ideal gas of structureless classical particles, a dilute gas of atoms, dilute gas of diatomic molecules, chemical equilibria in gases); Statistical Mechanical Theory of Phase Transitions (Ising model, lattice gas, broken symmetry and range of correlations, mean field theory, variational treatment of mean field theory, renormalization group theory, RG theory for the two-dimensional Ising model); Classical Fluids (averages in phase space, reduced configurational distribution functions, reversible work theorem, thermodynamic properties from g(r), measurement of g(r) by diffraction); Statistical Mechanics of Non-Equilibrium Systems (systems close to equilibrium, Onsager's regression hypothesis and time correlation functions, chemical kinetics, self-diffusion, fluctuation-dissipation theorem, response functions, absorption, friction and Langevin equation).
Chm 302: Quantum Chemistry
Text: Schatz, G.C.; Ratner, M.A. Quantum Mechanics in Chemistry; Prentice-Hall, 1994.
Review of Basic Concepts in Quantum Mechanics (fundamental definitions, eigenvalues and eigenfunctions, approximate methods, raising and lowering operators, two-body problems, electronic structure of atoms and molecules); Symmetry Considerations: Point Groups and Electronic Structure (group theory for point groups, applications of group theory to quantum mechanics, symmetry properties of many-electron wavefunctions); Symmetry Considerations: Continuous Groups and Rotations (introduction, continuous groups; the electronic structure of linear molecules, three-dimensional rotation group; angular momentum addition); Time-Dependent Quantum Mechanics (introduction, time-dependent Schrdinger equation; basis set solution, time-dependent perturbation theory, representations in quantum mechanics, transition probabilities per unit time); Interaction of Radiation with Matter (introduction, electromagnetic fields, interaction between matter and field, absorption and emission of light, light scattering); Occupation Number Representations (introduction, occupation number representation for harmonic molecular vibrations and quantized radiation fields, occupation number representations for electrons, Fermion field operators and second quantization, molecular electronic structure: model hamiltonians and occupation number representations, treatment of interacting electrons); Time-Dependent Approach to Spectroscopy: Electronic, Vibrational, and Rotational Spectra (introduction, thermal averages and imaginary time propagation, electronic spectra from time correlation functions, electronic spectra: time development of the correlation function approach, rotational, Raman, and magnetic resonance spectra, motional narrowing and stochastic motion); Density Matrices (introduction, density operators and density matrices: definitions and averages, representations and equations of motion, Examples: spin-1/2 particles, reduced density matrices, reduced density matrices for dynamical statistical systems, higher order corrections to the density matrix: pulsed spectroscopy.
Chm 306: Principles and Applications in Biophysical and Physical Chemistry
The interrelationships between structure, function, and mechanisms of biological macromolecules, principles of dynamics (including kinetics, reactivity, and transport) and structure (including thermodynamics, NMR, fluoescence, CD spectroscopy, and other applicable biophysical techniques.
Chm 310: Electronic Structure and Spectroscopy of Transition metal Compounds
Text: Drago, R.S. Physical Methods for Chemists, 2nd Edition; Saunders, 1992.
Symmetry and Point Groups* (Definition of symmetry, symmetry elements, point groups, space symmetry); Group Theory and Character Tables* (rules for elements that constitute a group, group multiplication tables, summary of properties of vectors and matrices, representations: geometric transformations, character tables, non-diagonal representations, decomposition formula, direct products); General Introduction to Spectroscopy* (radiation, energies, atomic and molecular transitions, selection rules, relaxation and chemical exchange influences on spectral line width, determination of concentration, isobestic points, Job's method, fingerprinting); Electronic Absorption Spectroscopy* (vibrational and electronic energy levels in a diatomic molecule, potential energy curves and spectra, assignment of transitions, oscillator styrengths, transition moment integral, derivation of some selection rules, spectrum of formaldehyde, spin-orbit and vibronic coupling contributions to intensity, mixing d and p orbitals, magnetic dipole and electric quadrupole contributions to intensity, charge transfer transitions, polarized absorption spectra, applications, optical rotary dispersion, circular dichroism, and magnetocircular dichroism); Electron Paramagnetic Resonance Spectroscopy* (nuclear hyperfine splitting, anisotropic effects); The Electronic Structure and Spectra of Transition Metal Ions (electron-electron interactions and term symbols, spin-orbit coupling in free ions, effects of ligands on the d orbital energies, symmetry aspects of the d orbital splitting by ligands, double groups, Jahn-Teller effect, magnetic coupling in metal ion clusters, survey of the electronic spectra of Oh complexes, calculation of Dq and b for Oh Ni(II) complexes, effect of distortions on the d orbital energy levels, structural evidence from electronic spectrum, s and p bonding parameters from the spectra of tetragonal complexes, angular overlap model, electronic spectra of oxo-bridged dinuclear iron centers, intervalence electron transfer bands, photoreactions); Magnetism (types of magnetic behavior, Van Vleck's equation, applications of susceptibility measurements, intramolecular effects, high spin-low spin equilibria, measurement of magnetic susceptibilities, superparamagnetism); Electronic Paramagnetic Resonance Spectra of Transition Metal Ion Complexes (interpretation of the g-values, hyperfine couplings and zero field splittings, ligand hyperfine couplings, EPR spectra of first row transition metal ion complexes, EPR of metal clusters, double resonance and Fourier transform EPR techniques).
*Background reading - review only.
Chm 312: Chemistry of the Main Group Elements and Organometallic Chemistry of Transition Elements.
Part I. Chemistry of the Main Group Elements.
Text: King, R.B. Inorganic Chemistry of Main Group Elements; VCH Publishers, 1995.
Preparations, bonding, structures, and reactivity of compounds of the main group elements with emphasis on members of the p-block groups. Specific topics include: Silicon, Germanium, Tin, Lead (general aspects, elements, anions and related binary compounds, hydrides and halides, silicates and related oxygen compounds, other oxygen compounds, organometallic derivatives, divalent compounds); Nitrogen (general aspects, isotopes and elemental nitrogen, nitrides, hydrogen compounds, oxides, oxoacids and oxoanions, nitrogen-halogen compounds); Phosphorus, Arsenic, Antimony, and Bismuth (general aspects, the elements, phosphides, arsenides, antimonides, and bismuthides, halides, oxides, sulfides and other chalcogenides, oxoacids and oxoanions, phosphorus-nitrogen compounds, organic derivatives, cationic chemistry in aqueous solutions); The Chalcogens (general aspects, the elements, compounds with O-O bonds, binary compounds of S and its heavier cogeners with H and metals, S-N compounds, halides, oxoacids and oxoanions, miscellaneous Se and Te compounds); Halogens and Noble Gases (general aspects, the elements, halides, halogen oxides, oxoacids and oxoanions, interhalogen and polyhalogen compounds: cations and anions, other halogen compounds, noble gas compounds); Boron (general aspects, the element and metal borides, boranes and related compounds, boron halides and their derivatives, B-O compounds, organoboron compounds, B-N derivatives); Aluminum, Gallium, Indium, and Thalium(general aspects, the elements and their alloys, aqueous solution chemistry of trivalent ions, oxygen derivatives of trivalent elements, halogen derivatives, hydride derivatives, other binary compounds, organometallic compounds, lower oxidation states than 3); The Alkali and Alkaline Earth Netals (general aspects, the elements, compounds, Be chemistry, Chemistry of Mg, Ca, Sr, and Ba); Zinc, Cadmium, and Mercury (general aspects, the elements, divalent compounds, organometallic compounds, oxidations states lower than 2).
Part II. Organometallic Chemistry of Transition Elements.
Text: Crabtree, R.H. Organometallic Chemistry of Transition Elements; 2nd Edition; Wiley, 1994.
Introduction (Werner complexes, the trans effect, soft versus hard ligands, the crystal field, the ligand field, back bonding, electroneutrality, types of ligands); General Properties of Organometallic Complexes (the 18-electron rule, limitations of the 18-electron rule, electron counting in reactions, oxidation state, coordination number and geometry, effects of complexation, different metals); Metal Alkyls, Aryls, and Hydrides and Related s-Bonded Ligands (the stability of transition metal alkyls and aryls, the preparation of metal alkyls, characterization and properties of metal alkyls, related s-bonded ligands, metal hydride complexes, bond strengths for classical s-bonding ligands); Carbonyls, Phosphine Complexes, and Ligand Subsitution Reactions (metal complexes of CO, RNC, CS, and NO, phosphines as ligands, dissociative substitution, the associative mechanism, redox effects, the I mechanism, and rearrangements in substitution, photochemical substitution, steric and solvent effects in substitution); Complexes of ¹-Bound Ligands (alkene and alkyne complexes, allyl complexes, diene complexes, cyclopentadienyl complexes, complexes of arenes and other alicyclic ligands, metalacycles and isoelectronic and isolobal replacement, stability of polyene and polyenyl complexes); Oxidative Addition and Reductive Elimination (three-center additions, SN2 reactions, radical mechanisms, ionic mechanisms, reductive elimination, oxidative coupling and reductive cleavage); Insertion and Elimination reactions involving CO, insertions involving alkenes, other insertions, a,b, g, and d eliminations).
Chm 314: Advanced Inorganic Reaction Mechanism
Ligand substitution reactions at a transition metal center: introduction to mechanistic concepts; relationships between activation mode and entering group, leaving group, steric crowding and charge; interchange mechanism for octahedral complexes; experimental basis for dissociative, D, classification; mechanism of stereochemical rearrangement; application of stereochemical data to the elucidation of acid and base hydrolysis mechanisms in octahedral complexes; substitution reactions in square planar complexes; linear free energy relationships in substitution reactions of square planar complexes; mechanism of oxidation and reduction reactions; reactions and mechanisms of transition metal organometallic compounds.
Chm 320: Synthetic Organic Chemistry
Alkylation of Nucleophilic Carbon, Enolates and Enamines (generation of carbanions by deprotonation, regioselectivity and stereoselectivity in enolate formation, other means of generating enolates, alkylation of enolates, generation and alkylation of dianions, medium effects in the alkylation of enolates, oxygen versus carbon as the site of alkylation, alkylation of aldehydes, esters, amides, and nitriles, the nitrogen analogs of enols and enolates - enamines and imine anions, alkylation of carbon nucleophiles by conjugate addition); Reactions of Carbon Nucleophiles with Carbonyl Groups (aldol condensation, condensation reactions of imines and iminium ions, acylation of carbanions, the Wittig and related reactions, reactions of carbonyl compounds with a-trimethylsilyl carbanions, sulfur ylides and related nucleophiles, nucleophilic addition-cyclization); Functional Group Interconversion by Nucleophilic Substitution (conversion of alcohols to alkylating agents, introduction of functional groups by nucleophilic substitution at saturated carbon, nucleophilic cleavage of carbon-oxygen bonds in ethers and esters, interconversion of carboxylic acid derivatives); Electrophilic Addition to Carbon-Carbon Multiple Bonds (oxymercuration, electrophilic sulfur and selenium reagents, addition to double bonds via organoboranes); Reduction of Carbonyl and Other Functional Groups (addition of hydrogen, Group III hydride-donor reagents, Group IV hydride donors, hydrogen atom donors, dissolving-metal reductions, reductive deoxygenation of carbonyl groups); Cycloadditions, Unimolecular Rearrangments, and Thermal Eliminations (cycloaddition reactions, dipolar cycloaddition reactions, [2 + 2] cycloadditions and other reactions leading to cyclobutanes, photochemical cycloaddition reactions); Organometallic Compounds of Group I and II Metals (preparation and properties of organolithium and organomagnesium compounds, reactions organolithium and organomagnesium compounds); Reactions Involving the Transition Metals (reactions of organocopper intermediates, reactions involving organopalladium intermediates, reactions involving rhodium, iron, and cobalt); Carbon-Carbon Bond-Forming Reactions of Compounds of Boron, Silicon, and Tin (organoboron compounds, organosilicon compounds, organotin compounds); Reactions Involving Carbenes and Nitrenes (structure and reactivity of carbenes, generation of carbenes, addition reactions, insertion reactions, rearrangement reactions, related reactions, nitrenes and related intermediates, rearrangements to electron-deficient nitrogen); Oxidations (oxidation of alcohols to aldehydes, ketones, or carboxylic acids, addition of oxygen at C=C, cleavage of C=C, selective oxidative cleavages at other functional groups, oxidation of ketones and aldehydes, allylic oxidation, oxidations at unfunctionalized carbon); Multistep Syntheses (protective groups, synthetic equivalent groups, synthetic analysis and planning, control of stereochemistry, illustrative syntheses).
Chm 322: Organic Reactive Intermediates.
Chm 326: Bioorganic Chemistry
An investigation of biochemical principles from the viewpoint of the organic chemist, fundamental and applied enzymology, enzyme inhibition, enzyme models, biosynthetic pathways, methodology for the study of biological transformations, molecular biology for organic chemists. Topics include: enzymes and enzymatic catalysis, acyl transfer to water: endopeptidases and exopeptidases, g-glutamyl transfers and amino transfers, phosporyl transfers, 1: phosphatases, ATpases and phosphodiesterases, kinases, nucleotidyl and pyrophosphoryl transfers, glycosyl transfers, enzymatic oxidations and reductions via apparent hydride transfers: nicotinamide coenzymes, flavin dependent dehydrogenases and oxidases, enzyme-catalyzed Aldol and Claisen condensations, enzymatic reactions requiring pyridoxal phosphate, enzymatic C1-group transfers requiring tetrahydrofolate or S-adenpsylmethinone, enzyme catalyzed alkylations involving prenyl-group transfer
Chm 330: Separation Science
Chm 334: Electroanalytical Chemistry
Introduction (basic electrical terms and concepts, electrode and electrochemical systems, general aspects of charge-transfer processes, reduction potentials and free energy, review of solution ionics: electrolytes and ionic strength: activity coefficients: standard states: development of the Nernst equation); Equilibrium Measurements (eletrochemical cell notation, redox reactions, calculation of cell potentials, batteries, fuel cells, sensors, potentiometry and ion-selective electrode: pH measurements and the glass electrode: cation-selective glass electrodes: solid-state membrane electrodes: ion-exchange and neutral carrier membranes: gas-sensing electrodes: potentiometric enzyme electrodes); Dynamic Electrochemical Measurements (review of basic kinetic expressions: the Arrhenius equation: the Butler-Volmer equation for electrode kinetics: the Tafel equation, mass transport to an electrode surface: diffusion: convection: migration, potential step and pulse techniques and their applications: chronoamperometry and chronocoulometry: normal pulse voltammetry: differential pulse and square wave voltammetry, polarography and anodic stripping voltammetry, cyclic voltammetry); Special Topics (ultramicroelectrodes, scanning probe microscopes: scanning tunneling microscopy: atomic force microscopy: other probe types: scanning electrochemical microscopy, spectroelectrochemistry, chemically-modified electrodes, biosensors).
Chm 336: Analytical Spectroscopy
Spectrochemical Information (radiation/matter interactions, nature of spectrochemical analysis: types of analyses: samples: spectrochemical phenomena: analysis of real samples, expressions of analytical information: calibration data: atomic and molecular spectra: optimization of the response function, evaluation criteria in spectrochemical techniques: practical considerations: automation and multiple species capability: interferences and selectivity: figures of merit); Spectrochemical Measurements (complete spectrochemical measurement, expressions of optical intensity: radiometric system: photometric system, spectrochemical methods: emission spectroscopy: absorption spectroscopy: luminescence spectroscopy: scattering methods, selection of optical information: wavelength selection: other selection criteria); Methodology in Spectrochemical Analysis (external standard calibration, systematic errors in spectrochemical methods: matrix errors: calibration errors: sample acquisition, preparation, and measurement errors, random errors in spectrochemical errors: determination of standard deviation in concentration: statistical statements: other considerations, sensitivity and detection limit, techniques for minimization of systematic and random errors: separations: saturation, buffer, and masking methods: dilution, matrix match, and parametric methods: methods of standard additions: methods based on optical encoding: chemical selectivity: instrument correction methods, automated spectrochemical measurements); Introduction to Atomic Spectroscopy (sample introduction and atomization: nebulizers: free-atom formation after nebulization: free-atom formation with discrete sample introduction, interferences in atomic spectroscopy: blank: analyte, electronic states of atoms: quantum numbers: coupling schemes: term symbols: selection rules and atomic spectra: additional splitting effects: statistical weights and partition functions, spectral line profiles: lifetime broadening: Doppler broadening: other causes of broadening: overall line profiles, spectral line intensities: thermal emission: absorption: atomic fluorescence); Introduction to Molecular Spectroscopy (molecular spectra, rotational spectra, vibrational spectra: pure vibrational transitions: rotation-vibrational transitions, electronic absorption spectra of diatomic molecules: electronic states: electronic transitions, electronic absorption spectra of polyatomic molecules: electronic states and transitions: electronic spectra: electronic band shapes and intensities, luminescence spectra: processes of deactivation: quantum efficiencies and power yields: luminescence lifetimes: quenching and excited-state reactions: band shapes: structural effects: environmental effects: polarization of luminescence); Ultraviolet and Visible Molecular Absorption Spectrophotometry (instrumentation, signal and noise expressions, apparent deviations from Beer's Law, methodology and performance characteristics, applications); Molecular Luminescence Spectrometry (instrumentation, signal and noise expressions, molecular fluorescence spectrometry, molecular phosphorescence spectrometry, chemiluminescence, lifetime and polarization measurements).
(24 hrs lecture, 5 ECTS credits)
Continuous assessment of lecture work; comprehensive final examination.
Text: Carey, F.A.; Sundberg, R.J. Advanced Organic Chemistry, part B: Reactions and Synthesis, 3rd Edition; Plenum Press, 1990.
A discussion of reactive intermediates in organic chemistry: carbanions, carbenes, carbonium ions, free radicals, photochemical excited states and other reactive species.
Text: Walsh, C. Enzymatic Reaction Mechanisms; Freeman, 1979.
Fundamental separation chemistry; practical aspects of chromatographic methods.
Text: Brett, C.M.; Brett, A.M.O. Electrochemistry; Oxford University Press, 1993.
Text: Ingle, J.D.; Crouch, S.R. Spectrochemical Analysis: Prentice Hall, 1988.