Chemical Physics-3H
Class Head: Dr. J.H. Dymond
CLASS HANDBOOK
COURSE DOCUMENTATION
1996/1997
Chemical Physics - 3 H
(Chemistry Component)
Course Head: Dr. J.H. Dymond
CONTENTS
Administration
Booklist
Aims and Objectives of Courses
Lecture Timetable
CHEMICAL PHYSICS-3H
SESSION 1996-7
ORGANIZATION
The Chemical Physics Course is organized jointly by the Departments of Chemistry and Physics
and Astronomy. The Class Heads are Dr. John H. Dymond (Chemistry), Tel: 0141-330-5949 (direct).
Room A5-21, and Dr. D. V. Land (Physics and Astronomy), Tel: 0141-330-4703, Room 251A. Please
contact them at any time if there are matters that you wish to discuss concerning the course.
ABSENCE FROM CLASSES
In the event of illness or other reasons for absence, both Dr. Dymond and Dr. Land should be
notified as soon as possible and, if appropriate, a relevant medical certificate should be submitted.
TIME-TABLE
A time-table for Chemical Physics-3H (Chemistry) is given on page 5. You should obtain an
additional timetable appropriate for Chemical Physics-3H (Physics) from the Department of Physics
and Astronomy. Please report any time-tabling problems immediately to Dr. Dymond and Dr. Land.
CHEMISTRY COMPONENT
TERM 1
Lectures: Tuesday - Friday 11am, in the Organic Lecture Theatre.
Tutorials: either Monday or Thursday, 10 am.
Attendance at Alchemist Club talks and local section RSC lectures, Thursdays, 4pm, is highly
encouraged. The Irvine Review Lecture at St. Andrews will take place on Friday 25th April, 1997;
the topic is Pharmaceutical Chemistry.
TERM 2 AND 3
Lectures: Thursday and Friday 11am, in the Organic Lecture Theatre, except weeks 14-17 Room A5-
07.
Laboratories: Physical Chemistry, six weeks in the period 18-25 inclusive, Monday, Tuesday and
Wednesday, 1-5pm.
CLASS CERTIFICATES
Admission to the Degree Examinations is contingent on the award of a Class Certificate. In order to
be certain of a Class Certificate, you are required to:
(a) regularly attend lectures and tutorials
(b) regularly attend laboratory sessions, and
(c) perform satisfactorily in the class examinations.
Note that: assessment of practical work throughout the session will contribute 12.5% to the
final assessment for the session with the written examination contributing 32.5%.
EXAMINATIONS
A class examination, to prepare you for the Degree Examination, will be held in week 13.
The Degree Examination consists of two 1 1/2-hour written papers on Chemical Physics -3H
(Chemistry). The department of Physics and Astronomy should be consulted for examination
requirements for Chemical Physics-3H (Physics), and for Mathematical and Computational Methods
for Physics-3 (Half). Marks obtained in the 3H June degree examinations contribute to the final -4H
M.Sci. Honours classification.
To gain admission to the Final Year, you must perform the work of this Level-3 course to the
satisfaction of the Head of Department..
SUMMARY OF LECTURE COURSES
Coordination Chemistry Dr Peacock
Molecular Symmetry Dr Hecht
Kinetics/Mechanism Dr Benniston
Quantum Mechanics of Atoms Dr Webster
Bonding Dr Webster
Kinetic Theory of Gases Dr Dymond
Crystallography Dr Muir
Radiochemistry/Catalysis Drs Stirling & Lennon
POLICY ON SUMMATIVE ASSESSMENT
All feedback on coursework used in assessment, including mid-year class exam/class test marks and
laboratory grades, is strictly provisional for your guidance only, and is subject to ratification by the
Board of Examiners and external examiners at the end of the academic year. You must retain all
copies of assessed work (lab notebooks, exam scripts, etc.) and have them available for inspection by
the examiners if requested at the end of the year. (You will be given reasonable advance warning
should this be required.)
INFORMATION TECHNOLOGY COURSES
The Chemistry Department runs two clusters of PC computers for 3rd and 4th year undergraduate use.
To use these you need a user name and password which are provided by Dr Tyler. To help you get the
most from these computers we offer a series of courses; attendance is not compulsory. The topics
covered are:
PCs for beginners (or for those who are a little 'rusty')
Word processing using Microsoft Word
Using the Internet
Using electronic mail.
Drawing molecules using Chem Window.
These courses are run by various staff members. The course are held on Friday afternoons and
coordinated by Dr. Gilmore. Other topics can be covered if there is sufficient student demand. The
third year physical chemistry laboratory includes courses on handling databases and on molecular
modelling which are also valuable skills for chemistry undergraduates to acquire.
CHEMICAL PHYSICS 3H and CHEMICAL PHYSICS 4H
RECOMMENDED TEXTBOOKS
Physical Chemistry, Second Edition, by R. A. Alberty and R. J. Silbey (John Wiley and Sons,
Chichester), 1992, £ 21.00.
Inorganic Chemistry, Second Edition, by D. F. Shriver, P. W. Atkins and C. H. Langford (Oxford
University Press), 1994, £ 19.50.
The Mechanisms of Reactions at Transition Metal Sites, by R. A . Henderson (Oxford Science
Publications), £ 4.99.
Chemical Bonding Theory, by B. C. Webster (Blackwell Scientific, Oxford), 1990, £ 19.95.
Introduction to Quantum Mechanics, by H. Bransden and C.J. Jaochain (Longmans), 1990, £23.99.
NOTE : ALL PRICES ARE SUBJECT TO CHANGE BY PUBLISHERS AT ANY TIME
Other books may be recommended by lecturers.
The following books are available in the Chemistry Branch Library
Group Theory in Chemistry and Spectroscopy, by T. S. Tsukerblat (Academic Press), 1994.
Chemical Applications of Group Theory, Third Edition, by F. A. Cotton (John Wiley and Sons,
Chichester), 1990.
Basic Solid State Chemistry, by A. R. West ((John Wiley and Sons, Chichester), 1990.
Structural Methods in Inorganic Chemistry, Second Edition, by E. A.V. Ebsworth, D. W. H. Rankin
and S. Craddock (Blackwell Scientific, Oxford), 1991.
Fundamentals of Molecular Spectroscopy, Fourth Edition, by C. N. Banwell (McGraw-Hill, London),
1994.
Heterogeneous Catalysis. Principles and Applications, G. C. Bond (Oxford University Press).
Crystal Structure Analysis: a Primer, Second Edition, J. P. Glusker and K. N. Trueblood (Oxford
University Press).
Title: Coordination Chemistry
Lecturer(s): Dr R D Peacock
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 and those of the second and third rows;
to explain the d«d spectra of transition metal ions.
Objectives:
1. Understand the basic concepts of coordination chemistry: d-orbital shapes, coordination
number and geometry, ligand substitution, chelate and macrocyclic effect, LFSE, kinetic and
thermodynamic stability, hard and soft behaviour.
2. Appreciate 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. Understand the bonding, chemistry and spectroscopy of the metal-metal multiple bond.
4. Understand the origins of the electronic spectra of transition metal ions.
5. Be able to use Tanabe-Sugano Diagrams (for the d2 and d3 configurations) to predict spectra
or to calculate the values of D and B.
6. Be able to solve problems involving coordination chemistry.
Outline:
Revision of level 1 and 2 chemistry. Basic concepts of transition metal and coordination
chemistry. Exemplification of first row chemistry. Contrast of first row and second and third row
chemistry. The metal-metal multiple bond.
Spectroscopy of d«d transitions.
Title: Molecular Symmetry
Lecturer(s): Dr rer nat Lutz Hecht
Aims: To demonstrate by means of worked examples how molecular symmetry arguments in the
context of the mathematical theory of groups can be exploited to deduce valuable information about
molecular properties and behaviour and how they can greatly simplify many important chemical
problems.
Objectives:
1. Define the terms symmetry element, symmetry operation and mathematical group, and
clarify their relationships.
2. Identify all the symmetry elements and symmetry operations of any given conformation of a
molecule, correctly assign it to a particular point group without any aids employing the Schoenflies
nomenclature, and sketch the correct conformation of a molecule for any given point group.
3. Construct group multiplication tables, determine matrix representations of group symmetry
operations and their characters, characterize character tables, distinguish between reducible and
irreducible representations, and indicate totally symmetric irreducible representations.
4. Reduce a general, reducible representation for any given point group using the reduction
formula and the corresponding character table, and construct appropriate sets of symmetry-adapted
basis functions from raw basis sets (such as atomic orbitals, atomic displacement coordinates or local
bond stretching coordinates) applying the projection operator method.
5. Specify the characters of direct product representations, and determine whether or not
quantum mechanical integrals will vanish identically as in the derivation of selection rules for
electronic and vibrational spectra or in molecular orbital theory.
Outline:
Symmetry arguments in the context of group theory provide a means of introducing
mathematical rigour into many important qualitative chemical problems such as the interpretation of
electronic and vibrational spectra, the simplification of quantum-mechanical calculations or the
existence of molecular properties such as permanent electric dipole moments and optical activity.
1. Definitions of molecular symmetry elements and of the associated symmetry operations they
generate.
2. Demonstration that the complete set of symmetry operations of a molecule forms a
mathematical group (a point group), Schoenflies nomenclature for molecular point groups, group
multiplication tables.
3. Representation of molecular symmetry operations by means of transformation matrices and
the associated irreducible representations and character tables, simple applications of character tables
to the determination of molecular dipole moments and optical activity.
4. Development of the general recipe for reducing representations, application to the
determination of hybridization schemes.
5. Introduction to the concept of symmetry-adapted functions, application of the projection
operator to generate sets of symmetry-adapted atomic orbitals for use as a basis in molecular orbital
calculations.
6. Formula for characters of direct product representations, vanishing integrals, applications to
molecular orbital calculations and spectroscopic selection rules.
7. Determination of the symmetry species of normal modes of vibration infrared and Raman
selection rules, stretching mode analysis to deduce the geometry of large molecules from the number
of infrared and Raman bands occuring in the appropriate stretching regions of the vibrational
spectrum.
Title: Inorganic Mechanisms/Photochemistry
Lecturer(s): Dr A C Benniston
Aims: To deal in depth with inorganic mechanisms in order that students will be able to identify
and comprehend how and why reactions occur in transition metal ion complexes. Introduce students
to the area of electrochemistry and photochemistry, and in particular cyclic voltammetry and
photoinduced electron transfer.
Objectives:
1. Inorganic mechanisms (5 lectures): Understand the difference between stability and lability
and how crystal field theory can be used to explain trends in ligand substitution in metal ion
complexes. Recognise parameters associated with the kinetics at metal ion centres, and how to
interpret them. Distinguish and classify inorganic reactions; for example substitution, electron-
transfer and ligand-activated reactions. Understand the difference between associative and
dissociative reaction mechanisms and what factors influence them.
2. Cyclic voltammetry (1 lecture): Have a general understanding of reactions at an electrode
surface, and how the difference between a reversible and irreversible process. Recognise the salient
features of a cyclic voltammogram and know how to obtain physical information using the Randle-
Sevcik equation.
3. Photochemistry (2 lectures): Have a general understanding of what terms mean including
donor/acceptor, triplet/singlet state and lifetime. Understand what is photoinduced electron transfer
between donor-acceptor molecules. Be able to describe what is electron transfer and energy transfer.
Know what photoinduced electronic processes can occur in transition metal ion complexes and give
examples (e.g. Ru (bipy)3 2+).
4. Overall: Be expected to apply what has been learnt to answer problems covering relevant
aspects of the preceding topics.
Outline:
Much of this third year course will cover new material and will be as descriptive as possible.
However, for the first part of this course it is essential that students re-acquaint themselves with
first/second year work; for example, crystal field theory, stepwise stability constants, hard and soft
acids/bases and general transition metal ion chemistry.
Title: Quantum Mechanics of Atoms
Lecturer(s): Dr B C Webster
Aim: To introduce elementary concepts of quantum mechanics.
Objectives:
1. Define the concept of probability using a one-dimensional model potential and describe
tunneling.
2. Specify the use of operators and in particular, the Hamiltonian.
3. Show the energy of H(1s1) is -½ hartree and specify Eh = .
4. Define expectation value and be able to apply this in simple cases.
5. Define and illustrate hydrogenic wave functions.
6. Write down the Hamiltonian for two electron atoms.
7. Apply the variation theorem.
Outline:
A particle in a 1D potential well, with infinite walls, and with finite walls; application to solvated
electrons. Specification of requirements for a wave function, probability and normalisation worked
examples of the same, definition and use of operators, application to H (1s1) ground state,
specification of expectation values, commuting operators and observables, angular momentum
operators, H atom atomic orbitals, discussion of centrifugal term and periodic table, energy level
diagram, variation theorem.
Title: Bonding Theory
Lecturer(s): Dr B C Webster
Aims: To develop an understanding of theoretical techniques and principles applied to
contemporary chemical situations and problem-solving skills applied to material previously unseen.
Objectives:
1. Write an electronic configuration for a diatomic molecule and sketch the shape of molecular
orbitals from 1sg to 3su including 1pu and 1pg.
2. State the variation theorem and understand the origin of the secular equations and secular
determinant.
3. Determine the Hückel orbital energy level diagram for unsaturated hydrocarbons, and
calculate the molecular orbital coefficients.
4. Calculate the p-charge densities and p-bond orders and use an order/length relation.
5. Construct a set of symmetry orbitals and understand how this basis set simplified the solution
of a secular determinant.
6. Write an electronic configuration for a polyatomic molecule using symmetry labels.
7. State the Walsh rules, draw a Walsh diagram for H2O and apply these rules to predict
molecular shapes.
8. Apply your problem-solving skills to previously unseen material as, for example, to the
detection and prediction of the shape of molecules in interstellar regions.
Outline:
Molecular orbitals for diatomics; variation theorem, L.C.A.O.M.O. approximation; solution
of the Hückel secular equations; the use of symmetry orbitals; electronic configurations for polyatomic
molecules; Walsh rules.
Title: Kinetic Theory of Gases
Lecturer: Dr. J.H. Dymond
Aims: to introduce students to the kinetic theory of gases
Objectives:
1. specify the kinetic model of a perfect gas.
2. use the kinetic theory to calculate the pressure of a perfect gas.
3. determine the mean value of discrete and continuous distributions.
4. understand the meaning of phase space, microstates and macrostates, and
follow the given statistical mechanical derivation of the generalized Maxwell-
Boltzmann distribution.
5. derive the Maxwell distribution of molecular speeds.
6. calculate the average speed, root-mean-square speed, and the most probable
speed of gas molecules.
7. calculate the frequency of collision of gas molecules with a surface.
8. calculate the rate of effusion of a gas through a hole, state Graham’s law of
effusion, and explain how it forms a basis for the separation of gas mixtures.
9. describe the Knudsen method for vapour pressure measurement.
10. describe how Maxwell’s speed distribution can be verified by molecular beam
studies.
11. describe the historical method of Perrin for determination of the Avogadro
number.
12. describe Brownian motion, understand what is meant by diffusion, and relate the
diffusion coefficient to the mean square displacement.
13. calculate the collision frequency and the mean free path and know how they vary
with temperature and pressure.
14. define thermal conductivity and viscosity and describe an experiment for the
determination of viscosity.
15. derive expressions for the transport properties in terms of the mean free path,
and hence explain their temperature and pressure dependence.
16. explain the p,V.T behaviour of real gases, and know the Principle of
Corresponding States and its significance.
Outline:
1. Introduction. The meaning of pressure and temperature; distribution functions.
General derivation of the ideal gas equation.
2. Discussion of phase space, microstates and macrostates of a system. Probability
of a given macrostate and derivation of a generalized distribution function.
3. The Maxwell normalised velocity distribution function. Properties of a Gaussian
distribution. The velocity distribution in a given direction.
4. Distribution of molecular speeds: average, most probable and root-mean-square
values.
5. Vapour pressures and the Knudsen experiment. Molecular beams and the
verification of the speed distribution law.
6. The barometric formula. Perrin’s experiment to determine the Avogadro number.
7. Collision frequency and the mean free path for gases. Experiments to determine
viscosity, thermal conductivity and diffusion coefficients.
8. Simplified kinetic theory of gas transport properties. The pVT properties of real
gases and the Principle of Corresponding States.
Title: Crystallography
Lecturer(s): Dr K W Muir
Aims: To introduce students to crystallographic symmetry, crystal structure analysis by diffraction
methods, and chemical applications of diffraction techniques.
Objectives:
1. Explain and employ the concepts used to describe the internal structure of crystals, including
the following terms: net, lattice, unit cell, non-primitive unit cell, space group, screw axis, glide
plane.
2. Explain the limitation of symmetry in nets and lattices and how this leads to a limitation in
the number of possible crystallographic point groups.
3. Know how beams of monochromatic X-rays can be obtained in the laboratory.
4. Understand and explain coherent elastic scattering of X-rays.
5. Derive and apply Bragg’s Law.
6. Define and use Miller indices.
7. Explain experimental methods used in diffraction studies and the nature of the results of such
experiments including the relationship between intensity and structure amplitude.
8. Understand and explain the terms atomic scattering factor and temperature factor.
9. Understand and explain the terms structure factor, structure amplitude and phase and know
the equation relating the structure factor to the positions of atoms within the unit cell of the crystal.
10. Be able to state the Fourier series expression for electron density distribution in a crystal and
know what is required before the Fourier series expression for electron density can be applied.
11. Understand and explain the nature of the phase problem.
12. Understand and explain the properties of the Patterson function and be capable of solving
heavy atom Patterson functions in common triclinic and monoclinic and orthorhombic space groups.
13. Understand and explain the nature of heavy atom methods of solving the phase problem.
14. Be capable of stating and explaining how crystal structures are refined.
15. Understand and explain the principles and main chemical applications of neutron diffraction.
16. Be aware of the main chemical applications of single crystal diffraction experiments.
17. Solve problems on the material presented in the lecture and associated laboratory courses.
Outline:
1. The Internal Structure of Crystals: Lattices, Unit Cells, Hermann-Mauguin Notation, Bravais
Nets & Lattices, Crystallographic Point Groups, Plane & Space Groups, Role of Symmetry in
Crystallography.
2. Geometry of X-ray Diffraction: X-ray Sources, X-rays, Matter & Diffraction, Bragg’s Law,
Experimental Methods.
3. Intensity of Bragg Reflections: Addition of Coherent Waves, Atomic Scattering Factors,
Temperature Factors, Unit Cell Scattering & the Structure Factor, Fourier Series Representation of
Electron Density, Space Group Determination.
4. Structure Analysis: The Phase Problem, Heavy Atom & Direct Methods.
5. Refinement: Agreement Indices, Difference Syntheses, Least-Squares Refinement.
6. Chemical Applications of X-ray Analysis: Biological Macromolecules, Organometallics,
Databases & Published Compilations, Absolute Configuration.
7. Neutron Diffraction: Principles, Experimental Considerations, Neutron Analysis, Chemical
Applications.
8. Charge Density Studies.
Practical experience of the concepts developed in the lecture course is provided by an
experiment in the physical chemistry laboratory.
Title: Radiochemistry and Catalysis
Lecturer(s): Dr D Stirling/ Dr D Lennon
Aims: To introduce students to the principles of radiochemistry and catalysis.
Objectives:
1. Know the principles of the production of artificial radionuclides by particle bombardment
and nuclear fission.
2. Understand the manner of growth of activity as a function of irradiation time for irradiation
in a constant neutron flux.
3. Understand how Szilard-Chalmers processes can be used to make sources of enhanced
specific activity by n.g reaction.
4. Understand how it is possible to discriminate between components of radioactive mixtures by
measurement of the energy of radiation.
5. Understand the function of a catalyst.
6. Physical and chemical adsorption processes, BET method for determination of surface area,
derivation of Langmuir isotherm for:
a) adsorption of a single substance.
b) competitive adsorption of two gases at a solid surface. Measurements of metal surface
area of a catalyst by chemisorption.
7. Have a knowledge of how tracers can be used in mechanistic studies of catalysis.
Outline:
Production of artificial radionuclides by nuclear fission and by particle capture, concept of
specific activity. Secular equilibrium - growth back to secular equilibrium when equilibrium is
disturbed by chemical separation of some components. Neutron activation for analysis and for
producing radionuclides for tracer studies; Szilard-Chalmers processes as a means of overcoming the
disadvantage that the product is often of low specific activity because it is isotopic with the target
material. Introduction to catalysis, physical and chemical adsorption, BET method for surface area
measurement, Langmuir isotherm, chemisorption for metal surface area measurement. Applications
of tracers to the study of catalytic processes.
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