* Your assessment is very important for improving the workof artificial intelligence, which forms the content of this project
Download Code: I1 Title: Heterogeneous Catalysis Lecturer: Prof S D Jackson
Survey
Document related concepts
Ionic compound wikipedia , lookup
Electron configuration wikipedia , lookup
Surface properties of transition metal oxides wikipedia , lookup
Reaction progress kinetic analysis wikipedia , lookup
Electrochemistry wikipedia , lookup
Chemical thermodynamics wikipedia , lookup
Two-dimensional nuclear magnetic resonance spectroscopy wikipedia , lookup
Woodward–Hoffmann rules wikipedia , lookup
Homoaromaticity wikipedia , lookup
Marcus theory wikipedia , lookup
Nuclear magnetic resonance spectroscopy wikipedia , lookup
Enzyme catalysis wikipedia , lookup
George S. Hammond wikipedia , lookup
Supramolecular catalysis wikipedia , lookup
Photoredox catalysis wikipedia , lookup
Transcript
Code: I1 Title: Heterogeneous Catalysis Lecturer: Prof S D Jackson Aims: To provide students with an introduction to heterogeneous catalysis Intended Learning Outcomes By the end of this lecture block students will be able to: 1. State the definition of catalysis and describe the process of heterogeneous catalysis in generic terms. (lecture 1) 2. Describe different heterogeneous catalyst preparation methodologies and be able to compare and contrast the catalysts produced by these methodologies. (relates to part of lecture 1 and all of lectures 2 and 3) 3. Illustrate the concepts of adsorption and catalytic sites and hence use these concepts in the development of reaction mechanisms. (relates to all of lectures 4, 5, 6 and 7) 4. Describe the processes of hydrogenation, dehydrogenation and base catalysis and be able to use the underlying concepts to explain why specific products are formed in a given reaction. (relates to all of lectures 5, 6 and 7) 5. Illustrate reaction mechanisms associated with a range of catalytic reactions. (relates to all of lectures 4, 5, 6, and 7) 6. State the main causes of catalyst deactivation and describe in specific terms how each can affect catalyst activity and selectivity. (relates to all of lecture 8) Outline: An introductory course in heterogeneous catalysis. The course will examine: A number of catalytic reactions looking at the adsorption process and the mechanism; It will cover the preparation of catalysts and their use in specific processes; The course will also study the analysis of data obtained from a catalytic reaction and how it can be used to determine the mechanism; Catalyst deactivation. Code: I2 Title: Main Group Chemistry Lecturer: Dr A Ganin Aims: The course builds upon the knowledge gained in years 1 and 2. It will expand on the ideas of bonding through the use of examples from main group chemistry. The student will also learn about some of the general chemistry of these elements (particularly groups 13 – 16) in addition to some detailed study of specific areas, including oxides, fluorides and boron hydrides. Intended Learning Outcomes: By the end of this lecture block students will be able to: Outline: 1. Apply molecular orbital theory as a description of bonding in simple discrete molecules. 2. Recognise situations when more unusual types of bonding occurs: Specifically; delocalised interactions such as 3 centre 2 electron bonds, the occurrence of p-p bonding in the main group compounds. 3. Apply their knowledge of the general basic chemistry of the main group elements and the trends in the chemistry of elements to the properties and reactivity of new compounds. 4. Show a detailed knowledge of some specific groups of compounds, including the chemistry of boron hydrides. 5. Apply Wade’s rules to boron hydrides, Zintl ions and cluster compounds. 6. Apply the knowledge and principles contained in 1 - 5 to unknown situations. Chemistry of some simple halides (group 13 -16), as electron rich and electron deficient compounds. Coordination geometry isomerism and fluxionality (e.g. in PF5). Using molecular orbital theory to understand bonding, structure and relativity in these compounds. Simple boron hydride chemistry and the semi-delocalised 3c-2e bonding picture. Complex boranes - closo, nido and arachno cages and the use of Wade’s rules in structure prediction. Extension of Wade’s rules to clusters and Zintl ions. The occurrence of homodinuclear and heterodinuclear p-p bonding in main group compounds; including group 14, 15, and 16, borazines and boron nitride. Code: I3 Title: Coordination Chemistry Lecturer: Prof. M Murrie Aims: To give an overview of the coordination chemistry of the transition elements; to emphasise the differences between the chemistry of the first row elements, the second and third row elements and the lanthanide elements; to explain the electronic spectra and magnetic properties of transition metal ions. Intended Learning Outcomes By the end of this lecture block students will be able to: 1. Explain the basic concepts of coordination chemistry: d-orbital shapes; coordination number and geometry; chelate effect; LFSE; kinetic and thermodynamic stability. 2. Identify the type of coordination chemistry shown by the first row elements and how and why the chemistry of the second and third row elements differs from this. 3. Recognise how the chemistry of the lanthanide elements differs from that of the transition elements. 4. Explain the origins of the electronic spectra of transition metal ions. 5. Summarise the magnetic properties of transition metal ions. 6. Solve problems involving coordination chemistry. Outline: Revision of level 1 and 2 chemistry; Basic concepts of transition metal and co-ordination chemistry; Exemplification of first row chemistry; Contrast of first row, second and third row chemistry and lanthanide element chemistry. Spectroscopy of dd and charge transfer transitions; Single-ion magnetic properties. Code: I4 Title: Organometallic Chemistry Lecturer: Dr D Price Aims: To consolidate and build on previous Level 1, 2 & 3 courses on the transition metals, to develop ideas on their organometallic compounds with respect to type, bonding and reactivity. Intended Learning Outcomes By the end of this lecture block students will be able to: 1. Describe the types of organometallic ligands found (both -donors and -acid ligands) and the basic reaction types associated with the more common ligands, i.e. oxidative addition, hydride migration, reductive elimination. Outline: 2. Describe the reasons why metal-alkyl complexes are unstable and the four main pre-requisites for the -elimination mechanism. Describe the experimental evidence for this mechanism. Explain how a knowledge of four main prerequisites for the -elimination mechanism can be applied to the synthesis of stable metal-alkyl compounds 3. Evaluate the formal oxidation states and d-electron counts of transition metal organometallic compounds, and be able to relate these to the types of ligand in the complex. Explain synergic bonding using simple molecular orbital theory and hence explain why certain ligands such as CO are able to stabilise metals in very low oxidation states. Describe the syntheses of some super-reduced carbonyl compounds. Describe the Dewar-Chatt-Duncanson model of bonding between an olefin and a transition metal and describe the experimental evidence for this model, in terms of bond distances and bond angles and barriers to rotation as observed in the NMR spectra. 4. Describe the types of complexes that hydrogen can form with transition metals, such as hydrido compounds, and compounds with dihydrogen ligands. Describe the experimental evidence for “non classical” hydrides, and be able to explain how T1 NMR measurements are used to characterise these dihydrogen complexes. 5. Describe the metal core structure of carbonyl clusters with delocalised metalmetal bonds, Evaluate the cluster electron counts and explain how they are related to boranes via extensions of Wade’s Rules. 18-electron rule; Properties and synthesis of organotransition metal compounds and their reaction types; Synergic bonding in -acid ligands like CO and simple olefins; Metal-metal bonds in carbonyl compounds and clusters; Metal-hydride compounds. Code: I5 Title: Solid State Chemistry Lecturer: Prof D H Gregory Aims: To advance understanding of the structure and properties of common inorganic solids. Intended Learning Outcomes By the end of this lecture block students will be able to: 1. Recognise the structures of some common inorganic solids including spinels. 2. Recognise the electronic properties of solids as applied to metals, semiconductors and insulators by application of band theory. Outline: 3. Recognise the factors affecting electronic conduction (band gaps) in inorganic solids. 4. Recognise point defects in solids and the relationship of defect concentration to temperature. 5. Recognise the various magnetic properties exhibited by solids and their origin. 6. Discuss and answer unseen questions, including calculations, on the relationship between structure and properties in inorganic solids. Study of the structures of various common inorganic solids; Electronic properties of solids investigated using band theory, p and n type semiconductors and factors affecting conduction in inorganic solids; Point defects and ionic conductivity; Magnetic properties of inorganic solids; Discussion of some practical applications of electronic and magnetic properties. Code: I6 Title: Biological Inorganic Chemistry Lecturer: Professor L Cronin Aims: To provide an appreciation of the role of the inorganic elements, primarily metal ions, in biological processes; to explain how chemists determine the structure. Introduction to metalloproteins. Intended Learning Outcomes By the end of this lecture block students will be able to: Outline: 1. Summarise the basic reasons for the incorporation of metal ions in life and be able to discuss the concentration of metal ions in the biosphere and living organisms. List examples of biological ligands, outline the metal ions used in life and their broader uses. 2. Write about examples of metals in proteins – how to study metalloproteins and to discuss modelling studies. Provide examples of choice and uptake and assembly of metal ions with a focus on Iron transport and storage and sequestration. 3. Explain the Electron transfer in proteins with respect to: Redox potentials, Aerobic respiration, Mitochondrial transport chain, Protection against oxygen and compare with Catalase Peroxidase BSOD. 4. Summarise how life facilitates oxygen transport and storage. 5. Understand and explain the process of photosynthesis including the light and dark reactions. 6. Illustrate the types of zinc(II)-based metalloenzymes and to discuss the reasons for life selecting zinc(II) and how some zinc-based metalloproteins are examined. 7. Write about the influence of Nucleic acids and zinc fingers in gene regulation with respect to structure and function, Metal ions and DNA structure, Metal ions and anti-cancer drugs – DNA metallation Introduction: What is biological inorganic chemistry and what areas does it cover; Study of Metalloproteins: Which metals are selected by life and their roles; Electron Transport and Oxygen Transport: The electron transport chain and the transport of oxygen; Photosynthesis: The mechanism and process of photosynthesis including dark and light reactions. Zinc-based metalloenzymes and metal based drugs: Lewis acids in biology and their roles, metal drugs in life. Code: O1 Title: Organic Spectroscopy Lecturer: Dr G. Bucher Aims: To gain knowledge of the physical basis of spectroscopic methods applied to organic chemistry. To be able to interpret spectra to and elucidate molecular structures. Intended Learning Outcomes By the end of this lecture block students will be able to: 1. Derive a molecular formula from elemental analysis data and calculate the degree of unsaturation. 2. State the physical basis of vibrational spectroscopy. 3. Evaluate vibrational spectra in order to elucidate the nature of functional groups present in the molecule. 4. State the physical basis of UV/Vis spectroscopy. 5. Evaluate UV/Vis data in order to elucidate the nature and structure of conjugated alkenes and arenes. 6. State the physical basis of mass spectrometry. 7. Evaluate mass spectra in order to elucidate molecular structures and fragmentation pathways. 8. State the physical basis of NMR spectroscopy. 9. Evaluate NMR spectra in order to elucidate molecular structures. 10. Derive molecular structures from a given set of spectroscopic information (IR, NMR, MS, UV/Vis, elemental analysis) Outline: This course will give an overview about spectroscopic methods frequently employed in the structural elucidation of organic compounds. Particular attention will be given on the practical analysis of spectra. Code: O2 Title: Organic Synthesis 1 Lecturer(s): Dr A Sutherland Aims: To revise and expand organic synthetic transformations and to apply these concepts to the synthesis of multifunctional organic compounds. The fundamentals of retrosynthetic analysis will also be introduced. Objectives: by the end of the course students should be able Outline: 1. To illustrate the different approaches for the synthesis of carbon/carbon double bonds including aldol condensations, eliminations and phosphorous based reactions. 2. To define the broad reactivity of alkenes and highlight important reactions such as, addition, ozonolysis, epoxidation, hydroboration and oxidation. 3. To apply the different methods of formation of carbon / carbon single bonds for the preparation of organic compounds. 4. To illustrate functional group interconversions of all the major functional groups. 5. To describe how chemoselectivity can be used for selective functional group manipulation in both oxidations and reductions. 6. To apply the rules of retrosynthetic analysis to target compounds and to design synthetic routes to these compounds. Synthesis of Alkenes: revise Aldol condensations and eliminations reactions; introduce the Wittig, Wadsworth-Emmons and Horner reactions; reduction of alkynes. Reactivity of Alkenes: revise addition reactions; ozonolysis; dihydroxylation; epoxidation and subsequent opening; hydroboration; Diels-Alder reaction; Oxidation using transition metals. Synthesis of C-C single bonds: traditional organometallic reagents (Li, Mg and Cu); Suzuki reaction. Functional group interconversions: oxidation of alcohols, aldehydes and ketones; Baeyer-Villiger oxidation of ketones; chemoselective reduction of carbonyl functional groups; reductive amination; activation of alcohols and subsequent reaction with C-, N-, O-, S- and Pnucleophiles. Case Study: Retrosynthetic analysis of a target compound and then design of a forward synthesis using some of the aforementioned techniques. Code: O3 Title: Controlling Stereochemistry Lecturer: Dr J. Prunet Aims: To introduce the principles of diasterereoselective and enantioselective synthesis. To describe methods of measuring enantio- and diastereoisomeric ratios. To demonstrate the importance of six-membered rings (whose properties will be revised) and conformational rigidity for conformational control, particularly in transition states. Intended Learning Outcomes By the end of this lecture block students will be able to: 1. Use accurately proper stereochemical conventions for drawing molecules which owe their chirality to a centre, an axis or a plane of chirality. 2. Identify the significance of enantiotopic and diastereotopic groups and faces. Recognise and provide examples of enantioselective and diastereoselective reactions. Rationalise selectivity in terms of diastereomeric transition states, which have different energies. 3. Recall chirally modified reagents such as chiral boranes, and explain their modes of action in straightforward cases. Recognise the importance of both steric and stereoelectronic factors in stereocontrol. 4. Define and use appropriately the terms enantiomeric excess (ee) and enantiomeric ratio (er). 5. Suggest analytical methods (spectroscopic and chromatographic) for measuring isomeric ratios. Conclude that determination of diastereomeric ratio is more straightforward than that of ee. Recognise that identification of the major isomer may not be straightforward but may be achieved by correlation or by crystallography. 6. Apply Felkin-Anh’s rule in nucleophilic addition to -chiral carbonyl compounds. 7. Identify chelation control in diastereoselective additions to - and -chiral alkoxy ketones and related compounds and explain the observed selectivity in such reactions. 8. Recognise the importance of conformational rigidity in controlling stereo- and sometimes regio-selectivity. Illustrate and explain the course of reactions on cyclohexenes and related compounds. 9. Understand catalytic enantioselective reactions. 10. Apply the above in unfamiliar situations. Outline: Introduction. Definitions, terms and conventions; drawing threedimensional molecules; chirality without a stereogenic centre; Reactions on achiral compounds. Achiral ketone + NaBH4; topism and prochirality; importance of asymmetric synthesis; enantiotopic faces; asymmetric reduction of prochiral ketones; (Ipc)2BCl and Alpine-boraneTM and their mode of action; enantiotopic groups; desymmetrisation and use of enzymes; Measuring the outcome. Enantiomeric excess; optical methods & their drawbacks; physical separation of enantiomers; resolution; chiral chromatography; spectroscopic methods; NMR on chiral compounds; chiral derivatising agents, Mosher’s acid chloride etc.; determination of absolute configuration; Reactions on chiral compounds. Nucleophilic addition to unfunctionalised -chiral ketones; threo/erythro, syn/anti and l/u nomenclature; Cram’s rule; Felkin-Anh rationalisation; chelation controlled attack; -chiral, -alkoxy carbonyl compounds; ester, amine and silyloxy substituents; -chiral, alkoxy carbonyl compounds; Six-membered rings. Reminder of chair conformations; half chair conformations of cyclohexene and its oxide; axial alkylation of 6-ring cyclic enolates; ring opening of cyclohexene oxides and related compounds; Chiral catalysts. Enzymatic resolution, asymmetric hydrogenation, enantioselective epoxidation and dihydroxylation, organocatalysis. Recommended Reading Clayden, Greeves, Warren & Wothers. Key phrases to look up: chirality; prochirality; pro-R and pro-S; diastereoselectivity; stereoselective reactions; cyclohexanes and cyclohexenes, conformations of; axial attack on cyclohexenes; hydroboration. Code: O4 Title: Mechanistic Organic Chemistry Lecturer: Prof R C Hartley Aims: To explain the factors that determine what products are formed in a reaction and the mechanisms and rates of formation; to introduce ways of determining mechanism and optimising reaction conditions. Intended Learning Outcomes By the end of this lecture block students will be able to: Outline: 1. Explain the concept of microscopic reversibility, the Hammond postulate, kinetics and thermodynamics, and be able to use the Arrhenius equation and Go=-RTlnK. 2. Construct and explain reaction co-ordinate and orbital energy diagrams. 3. Recall and construct curly arrow mechanisms for a variety of reaction types including substitutions at saturated centres (SN1, SN2 and intramolecular displacements) by various nucleophiles (including enolates), eliminations to form alkenes (E1, E2 and E1cB), and rearrangements. 4. Recognise orbital overlap and conjugation and so predict and explain the shape, relative thermodynamic stability and reactivity of molecules. 5. Recognise and explain steric and stereoelectronic effects and so predict and explain the shape, relative thermodynamic stability and reactivity of molecules. 6. Explain the role of orbital and electrostatic interactions in SN2 reactions. 7. Recognise the role of proximity and entropic effects, and construct curly arrow mechanisms for neighbouring group participation. 8. Construct and carry out calculations using rate equations 9. Explain and evaluate how temperature, concentration, solvent, and catalysts (in particular nucleophilic) affect the position of equilibrium and the rate of reactions and predict suitable conditions for proposed reactions. 10. Interpret mechanistic evidence and propose experiments for distinguishing between and determining mechanisms Revision of mechanisms of substitution at a saturated centre, elimination, and acyl substitution; Reaction coordinate diagrams, thermodynamics and kinetics, solvents, microscopic reversibility, Hammond postulate; Structural features affecting substitution and elimination reactions including conjugation effects, orbital alignment (eliminations and migrations), electronic strain, other stereoelectronic effects (hyperconjugation), HOMO-LUMO and electrostatic interactions (hard/soft nucleophiles), steric effects, entropic effects, proximity effects (ring size, neighbouring group participation, anchimeric assistance); Variables affecting substitution and elimination reactions including temperature, concentration, solvent, catalysts (nucleophilic); Determining mechanism of reaction through structural evidence (substrates, products, stereochemistry), kinetic evidence (order of reaction, rate changes). Code: O5 Title: Reactive Intermediates Lecturer: Dr G Bucher Aims: To provide a basic introduction to modern synthetic chemistry using radicals and carbenes. Intended Learning Outcomes By the end of this lecture block students will be able to: Outline: 1. Describe and illustrate the structure and stability of radicals and to recognise the principle of homolytic bond cleavage including how to draw radical mechanisms. 2. Describe and illustrate the many methods for initiating and mediating radical reactions and recognise the reagents used. 3. Describe chain reactions using tributyltin hydride and various functional group transformations using the reagent. Illustrate using the BartonMcCombie reaction, and reduction of thiohydroxamate esters. 4. Describe radical cyclisation reactions using curly-arrow mechanisms. Apply Baldwin’s rules and nomenclature. 5. Recall electron-transfer reactions. Illustrate the use of dissolving metals, samarium(II) iodide and low-valent titanium reagents (e.g. Birch reduction, ketyl-olefin cyclisations and pinacol couplings). 6. Describe and illustrate the structure and properties of carbenes (including metallocarbenes and carbenoids). 7. Describe synthetically useful reactions of carbenes. Illustrate the use of cyclopropanation, insertion and rearrangement reactions. (e.g. SimmonsSmith cyclopropanation, intramolecular cyclopropanation, the Wolff rearrangement (Arndt-Eistert homologation)). Properties and reactivities of important reactive intermediates, focussing on radicals and carbenes; The structure and stability of radicals and the principles of homolytic bond cleavage and radical mechanisms; Methods for initiating and mediating radical reactions, and the reagents used; Chain reactions using tributyltin hydride and functional group transformations (e.g. Barton-McCombie, reduction of thiohydroxamate esters) as will radical cyclisation reactions (Baldwin’s nomenclature); Electron-transfer reactions using dissolving metals, samarium(II) iodide and low-valent titanium reagents (e.g. Birch reduction of aromatics, ketylolefin cyclisations and pinacol couplings); Structure and properties of carbenes (including metallocarbenes and carbenoids) and the synthetically useful reactions of carbenes including, cyclopropanation, insertion and rearrangement reactions (e.g. SimmonsSmith, intramolecular cyclopropanation, the Wolff rearrangement (as part of the Arndt-Eistert process)). Code: O6 Title: Medicinal Chemistry Lecturer: Dr David France Aims: To illustrate the challenges associated with the discovery and development of new medicines. In particular, the concepts of pharmacokinetics and pharmacodynamics will be introduced. Several case studies will show the application of these principles to real-world systems. Intended Learning Outcomes By the end of this lecture block students will be able to: 1. Analyse a previously unseen structure to determine if it is “drug-like”. 2. Identify different potential biological targets for drug action, and evaluate the merits/problems associated with targeting them. 3. Differentiate between competitive and non-competitive enzyme inhibitors, and understand the kinetics associated with their use. 4. Define and explain the importance of IC50, ED50, LD50, TI, and the pharmacokinetic properties commonly referred to as ADME. 5. Explain how prodrugs and bioisosteres can sometimes overcome poor pharmacokinetic properties of a medicine. 6. Describe the entire process of drug discovery and development using real world examples such as migraine therapy, ACE inhibitors, anti-bacterial agents, anti-fungals, and anti-viral medications. Outline: Medicinal Chemistry background: the pharmaceutical industry, Types of biological targets. Pharmacodynamics: Enzyme kinetics (Michaelis–Menten and Lineweaver–Burk), reversible and irreversible inhibitors Pharmacokinetics: ADME properties, including liberation and toxicity, the role of bioisosteres and prodrugs. Case studies: o Indoles and Migraines: Fischer indole synthesis. o ACE inhibitors: background on hypertension, Discovery, mechanism, synthesis of ACE inhibitors. o Anti-bacterial agents: sulfa drugs and penicillins. Discovery, mechanism, synthesis. o Anti-fungals: background, selective ergosterol binders, inhibitors of ergosterol synthesis, Mannich reaction, imidazole containing drugs o Anti-viral medications: background on viruses. DNA and RNA viruses. Nucleoside analogues, and non-nucleoside analogues. Code: P1 Title: Quantum Mechanics and Mathematics for Chemists Lecturer: Dr Anna Stradomska Aims: To introduce the basic principles of quantum mechanics and illustrate how these concepts can be applied to a variety of chemical systems. The course will include the presentation of some elementary mathematical procedures necessary to derive and manipulate the mathematical expressions that define the quantum chemical concepts. The mathematics presented will also have application in other areas of the physical chemistry course. Intended Learning Outcomes By the end of this lecture block students will be able to: 1 Apply the mathematical concepts of differentiation, integration, differential equations and complex numbers to chemical problems. 2. Explain the concept of wave-particle duality and use it to interpret physical phenomena. 3. Recall the time-independent Schrödinger equation and explain its pivotal role in quantum chemistry. 4. Write the Schrödinger equation for simple potentials in 1, 2 and 3 dimensions. 5. Solve Schrödinger equation for simple 1-dimensional potentials. 6. Enumerate the properties of a wavefunction, and apply probabilistic interpretation of a wavefunction. 7. Write operators of a simple physical observables and use them to calculate expectation (average) values. Contrast the expectation value with possible outcomes of a single measurement. 8. State the Heisenberg Uncertainty Principle in qualitative and quantitative terms, and apply it to simple systems. 9. For simple model systems presented in the lectures: a) describe the model b) write the Schrödinger equation c) recall the mathematical form of the solutions of the Schrödinger equation d) sketch the wavefunctions and corresponding probability densities e) apply the model to calculate energy levels and spectroscopic transitions 10. Apply the above to previously unseen examples. Outline: Basic mathematical principles Principles of quantum mechanics Particle in a 1-dimensional box Vibrational motion Rotational motion Code: P2 Title: Symmetry and Bonding Lecturer(s): Dr Hans Senn Aims: The first part of this lecture block deals with the practical aspects of molecular symmetry and provides an introduction into group theory. These ideas are then applied to develop a bonding picture of polyatomic molecules in the context of molecular-orbital theory and to molecular vibrations. Intended Learning Outcomes By the end of this lecture block students will be able to: 1. Identify the point group to which a molecule belongs. 2. Explain the link between molecular symmetry and group theory. 3. Explain the meaning of characters and representations. 4. Construct reducible representations from atomic orbitals or displacement vectors and reduce them to a sum of irreducible representations. 5. Formulate how atomic wavefunctions combine to form molecular orbitals in diatomics. 6. Apply group theory to the construction of molecular-orbital diagrams of polyatomic molecules. 7. Interpret MO diagrams in terms of chemical bonding and reactivity. 8. Construct and interpret Walsh diagrams and explain the connection between molecular structure and electronic configuration. 9. Explain the origin of selection rules in electronic and vibrational spectroscopy. 10. Outline: Apply group theory to molecular vibrations and electronic transitions. • Concepts of symmetry; symmetry elements and symmetry operations; point groups. • Fundamentals of group theory; reducible and irreducible representations; reduction of reducible representations; identification of symmetry-adapted linear combinations. • Review of basic molecular-orbital theory; symmetry in MO theory. • Construction and interpretation of MO diagrams and Walsh diagrams. • Symmetry properties of electronic transitions and molecular vibrations; selection rules. Code: P3 Title: Chemical Kinetics Lecturer: Prof D Lennon Aims: To illustrate how reaction kinetics can be applied to a number of disparate chemical systems. The course builds on principles introduced in the kinetics course presented in Chem-1. The course will illustrate the importance of kinetics in chemical synthesis, the elucidation of reaction mechanisms and catalysis. Intended Learning Outcomes By the end of this lecture block students will be able to: Outline: 1. State why reaction kinetics are important throughout all branches of chemistry. 2. State the empirical treatment of reaction rates and to recall the linkage between reaction kinetics and mechanism. 3. Derive and manipulate kinetic schemes for a variety of chemical reactions. 4. Calculate reactant (or product) concentrations as a function of time. 5. Recognise the versatility of pseudo-order reaction conditions. 6. Derive and manipulate kinetic reaction schemes for complex reactions: concurrent and consecutive. Recognise the versatility of the steady-state approximation. 7. Recognise how the choice of a solvent may affect reaction rates. 8. Describe the concepts of transition state theory and apply it to understand how the choice of solvent may influence reaction rate. 9. Demonstrate the importance of mass transfer properties to affect reaction rates and product selectivity in heterogeneously catalysed liquid phase reactions. Empirical treatment of reaction rates; Pseudo-order reactions; Complex reactions: concurrent and consecutive; approximation; Solvent effects on reaction rate; Heterogeneous catalysis. 8 lecture course + 2 tutorial sessions + 1 laboratory session. steady-state Recommended Book P. Atkins and J. de Paula, Atkins’s Physical Chemistry, Oxford University Press, 9th Edition (2010) ISBN: 978-0-19-954337-3 Code: P4 Title: Electronic Spectroscopy and Photochemistry Lecturer: Prof. M Kadodwala Aims: The objective of the course is to provide a general overview of electronic spectroscopy and photochemistry Intended Learning Outcomes By the end of this lecture block students will be able to: 1. 2. 3. 4. Outline: Summarise the basic principle of electronic spectroscopy in atoms and molecules Explain how the electronic states of atoms and molecules can be described using term symbols Recall specific examples of the application of electronic spectroscopy in atoms and molecules Summarise the basic physical and chemical principles of photochemistry will be introduced 5. Explain how the analysis of information on the rates of reactions can provide an improved understanding of photochemical processes 6. List and discuss examples of applications of photochemistry The principles of describing electronic structure in atoms and molecules The underlying principles of electronic spectroscopy Applications of electronic spectroscopy Photochemical principles Photochemical kinetics Applications of photochemistry Code: P5 Title: Magnetic Resonance Lecturer: Dr Smita Odedra Aims: To introduce the physical basis of NMR spectroscopy and the interactions determining the appearance of NMR spectra in solution. To describe modern experimental methods for obtaining high-resolution NMR spectra. To give an introduction of the challenges faced in obtaining high-resolution solid-state NMR spectra. To describe the significance and process of relaxation. To compare NMR and EPR/ESR and highlight their similarities and differences. Intended Learning Outcomes By the end of this lecture block students will be able to: 1. Describe the physical basis of NMR spectroscopy. 2. Describe the origin and predict the influence that major interactions (the chemical shift, J-couplings, the dipolar interaction and quadrupolar interaction) will have in determining the appearance of NMR spectra. 3. Describe the time-domain or Fourier transform method of acquiring NMR spectra and state its advantages over older techniques. 4. Describe how molecular dynamics and conformational exchange will modify the appearance of NMR spectra. 5. Discuss mechanisms that influence NMR relaxation. 6. Describe the physical basis of EPR/ESR spectroscopy and the interactions that determine the appearance of the spectra; compare these with NMR spectroscopy. 7. Apply the theory and techniques introduced during this course to related exercises. Outline: This lecture course will consist of a physical chemist’s view of NMR spectroscopy and of its sister technique EPR (or sometimes ESR) spectroscopy. The emphasis will be on understanding the method (both its quantum-mechanical origins and its experimental practicalities) and the spectra it produces, rather than on its everyday empirical use for determining molecular structure. Reading: Physical Chemistry, Peter Atkins and Julio de Paula, Oxford University Press. Nuclear Magnetic Resonance, Peter J Hore, Oxford Chemistry Primers (no. 32). Understanding NMR Spectroscopy, James Keeler, Wiley, Chichester, 2005. ISBN: 978-0470017876 Code: P6 Title: Biophysical Chemistry and Diffraction Lecturer: Dr Adrian J Lapthorn Aims: To discuss the noncovalent intermolecular forces in complex condensed systems and how this applies to the stabilisation of biomolecular structures and interactions. To describe a number of physical techniques and assess their applicability to answer particular questions about the stability, form and function of proteins. To give a detailed overview of diffraction theory and highlight the information it provides about structure of materials. Intended Learning Outcomes By the end of this lecture block students will be able to: 1. Identify noncovalent interactions; namely, different types of electrostatic interactions, hydrogen bonding and hydrophobic interactions. 2. Know what the “Levinthal Paradox” is and be able to calculate the effect for a 100 amino acid protein. 3. To be able to illustrate that there is a balance of opposing thermodynamic forces involved in protein folding and other macromolecular interactions. 4. Using suitable equations that must be recalled, calculate molecular interaction energies and thermodynamic properties of proteins. 5. To identify suitable experimental techniques for the study of macromolecular conformations and interactions. Explain the fundamental principles of each technique and state how they would apply to a given problem. 6. Explain how beams of monochromatic X-rays and neutrons can be obtained and recall the different ways in which X-rays can interact with matter at the atomic level. 7. Explain what is meant by Miller indices, State Bragg’s Law and use them to calculate the scattering angle of a given reflection. 8. State what are atomic scattering factors and temperature factors, structure factor, structure factor amplitude and phase and explain how they are related. Recall that the observed structure factor amplitude depends on the positions of atoms within the unit cell of the crystal. 9. Identify methods used to solve the crystallographic phase problem and summarise how the methods are applied, listing the assumptions implicit to each method. 10. List the necessary steps and calculations required to solve and then complete a single crystal X-ray structure. Explain what is involved in each of the steps and recognise why the order of the individual steps is important. 11. Explain the differences between single crystal neutron and X-ray experiments. Recognise the different forms of diffraction and summarise their uses. Outline: Non-covalent intermolecular forces; Thermodynamics of macromolecules; Protein folding; Ligand binding; Molecular recognition; Biophysical techniques for determining the energetics of biomolecular processes. Source of X-rays; interaction of X-rays with matter; Braggs law; diffraction intensities; Miller indices; phase problem; atomic scattering factors; effect of atomic vibration; structure factor calculations; Fourier transforms; Patterson methods and Direct methods; refinement and completion of a structure; Powder diffraction and neutron diffraction