Core Chemistry 3 (level 4)

CHEM40221 Core Chemistry 3 (level 4) 10 Semester 1 Undergraduate Level 4 Cristina Trujillo del Valle Unit coordinator Simon Webb Unit coordinator Neil Burton Unit coordinator Andrew Horn Unit coordinator 1 FHEQ level (Framework for Higher Education Qualifications) ' Masters/Integrated Masters P4 ' European Credit Transfer & Accumulation System Rating : 5.0 Knowledge covering the 'principles of modern physical chemistry' is presented primarily in lectures. This material is reinforced in problem-based workshops, in which students are expected to participate and demonstrate their understanding of the topics. Statistical Thermodynamics (Dr Cristina Trujillo, 6 lectures)<ul> <li>Introduction. Boltzmann distribution.</li> <li>Molecular partition function (translational, rotational, vibrational, electronic)</li> <li>Molecular energy.  Internal Energy.  Entropy.</li> <li>Ensembles.  Canonical partition function.  Helmholtz energy.  Pressure.</li> <li>Gibbs Energy.  Equilibrium constant.</li> <li>Example class.</li></ul>Chemical Properties from Potential Energy Surfaces (Dr. N.A. Burton, 7 lectures)<ul> <li>potential energy surfaces (PES): Born-Oppenheimer approximation; revision of stationary points & reaction coordinate for collinear triatomic reactions; reaction dynamics on a PES; early and late transition states; reactant/product energy partitioning; use in chemical lasers</li> <li>thermodynamic properties derived from PES: thermal corrections and internal energy, enthalpy and entropy; adiabatic and diabatic descriptions of the PES; Evans-Polanyi model; Hammond’s postulate; non-adiabatic dynamics</li> <li>transition state theory and the Eyring equation: assumptions, derivation, symmetry and statistical factors, criticisms, tunnelling; kinetic isotope effects; detailed application to the F + H2 reaction.</li></ul>Photochemistry (Prof A.B. Horn, 5 lectures)<ul> <li>the basic laws of photophysics and photochemistry: absorption, stimulated emission and spontaneous emission; electronic excited states described using PE surfaces; the Born-Oppenheimer and Franck-Condon principles revisited; spin multiplicity, photophysical processes (luminescent and non-radiative); Jablonski diagrams; quantum yields; quenching and the Stern-Volmer approach.</li> <li>excited states and their role in chemistry and spectroscopy: fates of an excited state; photodissociation; Norrish reactions; atmospheric photochemistry - stratospheric ozone and tropospheric oxidation via OH radicals; photochemistry in unsaturated organic species, Woodward-Hoffman correlation rules;</li> <li>experimental measurement of photochemical processes: light sources for photochemistry and spectroscopy; incandescent sources; lasers and LEDs; synchrotrons; pulsed radiation; principles of high-resolution and ultrafast spectroscopy.</li></ul>Modern Physical Organic Chemistry: (Dr S. J. Webb, 6 lectures)<ul> <li>The relationship between free energy change, equilibrium constant and reactivity</li> <li>The physical concepts necessary for the design of experiments to test or establish a reaction mechanism, and the application of physical methods to mechanistic problems</li> <li>The effects of structural variation and change of reaction conditions on organic reactivity</li> <li>Types of supramolecular interactions and their relative strengths</li> <li>Some applications of supramolecular chemistry</li></ul> This unit aims to: present core physical chemistry courses on statistical thermodynamics, potential energy surfaces, photochemistry and physcial-organic chemistry. On successful completion of the course students should be able to:<ul> <li>explain the key steps in teh derivation of the Boltzmann distribution;</li> <li>select and apply the tools of statistical thermodynamics to predict gaseous properties;</li> <li>apply the concept of potential energy surfaces to explain the basis of chemical reaction dynamics for small molecules;</li> <li>select and apply concepts in transition-state theory and the Eyring equation to predict and explain dynamical and kinetic behaviour in small molecules;</li> <li>explain the intensity of absorption of light and the probability of primary photophyscial processes using simple quantum-mechanical arguments and Jablonski diagrams;</li> <li>rationalise simple photochemical processes and reaction in terms of electronic excited states;</li> <li>identify appropriate light sources for spectroscopic and photochemical measurements based on their characteristics and properties;</li> <li>explain the detailed nature of the relationship between free energy, equilibrium constant, and reactivity in the context of organic chemistry;</li> <li>design experiments to measure and rationalise chemical reaction mechanisms;</li> <li>apply the principles of physical and physical-organic chemistry to explain and rationalise the structure and properties of topical supramolecular materials.</li></ul> Students should be able to: <ul> <li> use statistical thermodynamics to predict gaseous properties</li> <li> understand the use of potential energy surfaces to study reaction dynamics</li> <li> appreciate the synergy of kinetics and thermodynamics</li> <li> understand the interaction of light with matter</li> <li> understand modern experimental methods to study reaction dynamics</li> <li> understand the theoretical framework of NMR spectroscopy</li> </ul> Knowledge covering the ‘principles of modern physical chemistry’ is presented primarily in lectures.  This material is reinforced in tutorials, in which students are expected to participate and demonstrate their understanding of the topics. <ul> <li> Problem-solving skills, numeracy and mathematical skills, analytical skills</li> </ul> 1 Written exam 100% Students will attend three problem-based workshops during the course, at which they will discuss and work on (with supervision) questions based on the taught material. N <ul> <li>P Atkins and J de Paula, Atkins’ Physical Chemistry (10th Ed), OUP, 2014</li> <li>A. Maczek, Statistical Thermodynamics, Oxford Chemistry Primers, 58, OUP, 1998</li> <li>C.E. Wayne and R.P. Wayne, Photochemistry, Oxford Chemistry Primers, 39, OUP, 1996</li> <li>J.I Steinfield, J.S Francisco & W.L Hase, Chemical Kinetics and Dynamics, Chapters 7 & 10.</li> <li>H. Maskill, The Physical Basis of Organic Chemistry OUP, 1985. ISBN 9780198551997</li> <li>E.V. Anslyn and D. A. Dougherty, Modern Physical Organic Chemistry (University Science Books, 2006) ISBN 9781891389319</li> <li>J W Steed and J L Atwood, Supramolecular Chemistry (Wiley, 2000) ISBN 0471987918</li> <li>P Beer, P Gale and D K Smith, Supramolecular Chemistry, OUP, 1999. ISBN 9780198504474.</li></ul> Assessment written exam 2 Lectures 24 Tutorials 3 0 71