This module covers several subjects of physical chemistry. Basic concepts of thermodynamics and kinetics, as introduced in Year one, are to be reinforced and extended in semester one. Quantum mechanics is introduced in a formal manner in Semester two.

The aims of the module are:

• To explain the application of the 1st and 2nd laws of thermodynamics to chemical reactions.
• To reinforce the basic ideas on factors affecting the rates of chemical reactions and quantify the kinetics.
• To provide an understanding of the basic concepts of quantum mechanics.
• To show how to apply the methods of quantum mechanics to simple systems .
• To show how molecular energy levels, spectroscopic transitions and selection rules arise. 

By the end of the module, students should be able to:

1. Discuss the difference between ideal and real gases.
2. Discuss the 1st and 2nd laws of thermodynamics in the context of chemical reactions.
3. Carry out thermochemical calculations involving enthalpy, entropy and Gibbs free energy.
4. Calculate equilibrium constants from thermodynamic data.
5. Describe and compare different experimental techniques for observing chemical kinetics.
6. Analyse experimental data for the determination of  reaction orders and rate coefficients, using appropriate methods depending on the type of data available.
7. Derive and apply rate equations and integrated rate equations for 0th, 1st and 2nd order reactions.
8. Show an understanding of activation barriers and apply the Arrhenius equation.
9. Describe qualitatively and quantitatively the kinetics of simple parallel, consecutive, and equilibration reactions.
10. Apply the steady state approximation.
11. Demonstrate an understanding of the concepts of quantum mechanics.
12. Apply the methods of quantum mechanics to simple systems.
13. Show an understanding of molecular energy levels and the forms of spectroscopy which involve transitions between them.
14. Use mathematical procedures and graphs for quantitative data analysis and problem solving.
15. Present and discuss the solution to problems in a small-group environment.

Thermodynamics

• Revision of material in Chem152: ideal gas equation, first law of thermodynamics, heat & work, enthalpy, Hess' law cycles, entropy, Gibbs energy, equilibrium constant and its temperature dependence.
• Real gases, virial and van der Waals equations of state.
• Examples of calculations using tables of thermodynamic data. Use of bond energies to predict U and H for chemical reactions.
• Heat capacity at constant volume or pressure, temperature dependence of internal energy and enthalpy.
• Second law of thermodynamics, statistical description of entropy.
• Dependence of entropy on temperature and pressure, third law of thermodynamics.
• Gibbs free energy, changes at constant temperature or pressure.
• Equilibrium constant K, relation to Gibbs free energy, variation with temperature.

Kinetics

• Revision of material in Chem152: Chemical reaction rates, rate equation, reaction orders, half life, activation energy barriers and Arrhenius equation, elementary step, rate-determining step & reaction mechanism, catalysis.
• Integrated rate equations.
• Experimental techniques for measuring reaction rates.
• Simple collision theory, activation energy, potential energy barriers, transition state. Steric hindrance.
• Parallel reactions.
• Consecutive reactions. The rate determining step. Steady state approximation.Pre-equilibrium.
• Reverse reaction and relaxation towards equilibrium.
• Collisional activation and deactivation. Lindemann-Hinshelwood mechanism.
• Diffusion-controlled reactions.
• Examples of complex reactions: Chai n reactions.

 Quantum mechanics

• Basic postulates of quantum mechanics and their interpretation, including: wave-functions, Born interpretation and Heisenberg uncertainty relations.
• Methods of quantum mechanics including: properties of operators and the relationship to physical observables, eigenvalue equations and expectation values.
• The Hamiltonian operator and the time-independent Schrödinger equation.
• Examples including: particle in a one-dimensional box (eigenvalues, wavefunctions, applications), tunnelling and approximate tunnelling rates.
• Quantum description of atomic and molecular energy levels.
• Born-Oppenheimer approximation: timescales for motion, potential energy curves, energy regimes.
• Bonding in simple molecules. 

Spectroscopy 

• Quantum description of spectra formation: transition probabilities, dipole moment operator, selection rules. Diatomic examples.
• Electronic Transitions: Potential Energy Surface and separation of electronic and nuclear motion.  Correlation diagrams for diatomic molecules.  Molecular term symbols and the non-crossing rule.  Selection rules for electronic transition; intensities (allowed/forbidden transitions), Franck-Condon factors, vibrational structure.
• Dissociation induced by electronic transitions:  Bound - bound and bound - free (continuum) transitions.  Predissociation (collisional or spin-orbit induced).
• Lasers: Principle of laser action and applications.

This module consists of 33 lectures (50 minutes), to be complemented by three revision lectures at the end of term.  The material presented at the lectures and its application for solving problems is supported by six 1-hour tutorials given over the two semesters at times to be published.  Students are expected to prepare the answers to tutorial problem questions before the tutorials, discuss them during the tutorials and submit answers to assignment problem questions after each tutorial.

P. Atkins, J. de Paula:Atkins’ Physical Chemistry – 7^th ed., Oxford University Press