The aims of this module are to present the essential mathematical and physical background needed to explain key concepts in physical chemistry. The first part of the module therefore provides the student with the essential mathematical treatments and machinery required to understand the concepts in the latter part of the module. The module aims to provide the student with an understanding of how properties and events at the atomic level lead to changes and processes that can be measured at a macroscopic level.

Knowledge

1. describe Newton’s laws of motion and demonstrate their importance in conservation of momentum;
2. distinguish between work done, energy and power, specifically knowing the importance of potential energy, kinetic energy and conservation of energy;
3. know about the early mysteries of classical mechanics, including the nature of light, the nature of matter, UV catastrophe, and the quantum hypothesis as proposed by Planck; 
4. relate the failings and limitations of classical mechanics to describe the properties of particles at the atomic scale;
5. describe simple harmonic motion and the modes of oscillators for diatomic and linear triatomic molecules;
6. describe the behaviour of gases in terms of molecular properties, recall the Ideal Gas Law, the fundamental  assumptions it makes and modifications thereto for non-ideality (van der Waals), gas diffusion and Graham’s Law;
7. know the importance of Maxwell-Boltzman velocity and speed distributions;
8. state the rate equation for a given reaction and distinguish between molecularity and order of reactions, recalling the integrated rate equations for 1st , 2nd and zero order reactions;
9. describe the effect of temperature on reactions, recalling the Arrhenius equation and its relationship with the Boltzmann distribution;
10. describe the collision theory of reaction rates and be aware of improvements to it;
11. describe methods used to measure rates of reaction at different timescales;
12. state the relationships between frequency, wavelength and energy, and list the regions of the electromagnetic spectrum arranged in order of energy;
13. describe absorption and emission processes and label lines in the H atom spectrum;
14. discuss electronic, vibrational, rotational and translational excitation of molecules and select appropriate regions of the spectrum for each;
15. know the classification of molecules in rotational spectra;
16. know the equations determining energy levels in a simple harmonic oscillator and for a linear rotor;
17. describe the diffraction of light and of electrons with awareness of the wave-particle duality;
18. state the first and second laws of thermodynamics, and be able to explain the difference between work and heat, and between reversible and non-reversible processes;
19. define what a state function is and give examples;
20. define the concept of enthalpy and explain how it can be measured, specifically enthalpies of fusion, sublimation, ionisation, dissociation;
21. apply Hess’s law and use Born-Haber cycles;
22. estimate reaction enthalpies from average bond energies;
23. define entropy in relation to chemical reactions;
24. explain how entropy is measured and its significance in chemical reactions;
25. rationalise and predict the sign of an entropy change for a chemical or physical transformation;
26. define the standard Gibbs free energy and explain its relationship to equilibrium constants.

 Understanding

1. understand how a few basic rules or ‘laws of nature’, such as Newton’s Laws of motion, demonstrated that disparate phenomena in nature could be explained in simple terms;
2. understand how periodic motion, a common form of mechanical behaviour, and its oscillatory characteristics, can be used to understand bonding and energy levels;
3. understand how classical mechanics can be generally used to derive expressions for the pressure and temperature of a gas in terms of the mass and velocity of its constituents;  
4. understand how reaction rates are dictated by concentration, reaction order and temperature, advancing to more complex kinetic processes such as enzyme kinetics;
5. understand how spectroscopy can reveal important details of the structure of atoms and the bonding in molecules;
6. understand how different regions of the electromagnetic spectrum yield different types of information on the properties of atoms and molecules;
7. understand how thermodynamics is concerned with the study of macroscopic systems or bulk assembles, rather than individual molecules;
8. understand how and why changes in entropy and enthalpy of a substance accompany changes in phases (phases equilibria).  

33 1-hour lectures, 30 (10 x 3) hours of practical work, 4 1-hour tutorials

Intellectual Skills:

The student will be able to show some experience in linking formal equations to the obserevd behaviour of matter.

Chemistry-specific skills

The student will be able to:

1. interpret experimental observations in terms of the molecular properties of the system;
2. use measurements of quantities such as heat, composition and pressure to determine thermodynamic parameters, and to construct simple phase diagram;
3. use integrated rate equations, initial rates and half-lives to determine reaction orders and hence determine activation energy and pre-exponential factor from experimental data for 1st, 2nd and zero order reactions;
4. measure and interpret electronic, vibrational and rotational spectra;
5. carry out standard experimental techniques in connection with determination of thermodynamic and electrochemical quantities;
6. show further development in the skill of extracting fundamental information from experimental results.

Transferable skills

The student will be able to:

1. develop an appreciation of the requirement for accuracy and precision in obtaining, recording and reporting experimental measurements;
2. experience the use of spreadsheets to evaluate experimental data;
3. use qualitative arguments to develop a theoretical model of a process;
4. use quantitative measurements to verify or disprove theoretical models.

The module will be assessed in a number of ways including coursework (class tests or workshops), formal exam in the Spring examination period, and through numerous written reports of the practical work. The tutorials will provide the platform to explore questions around the lecture material, and so to enhance the students’ understanding of the material and to link the concepts together. Transferable skills will be primarily assessed through the laboratory work. 

Foundations of physical chemistryI (Autumn semester)

An introduction to Physical Chemistry; The states of matter, physical state, forces, energy, pressure, temperature, amount of substance, units.

Describing motion; basic ideas, equations & principles; Vectors & scalars, types of forces, describing motion, equations of motion, projectiles, Newton’s Laws and momentum, The first law, second law, third law, impulse, conservation of momentum,  Work, energy and power,  Work done, power, kinetic energy & potential energy, interchange between KE & PE, elastic and inelastic collisions,

Circular motion & simple harmonic motion; Measuring rotation and angular speed, centripetal acceleration, moving in horizontal circles, free oscillations, damped oscillations, forced oscillations, coupled oscillators and normal modes.

Energy & change: State functions and non-state functions (work, heat, energy etc), 1^st law, reversible and non-reversible changes, enthalpy changes, 2^nd law, entropy, standard molar Gibbs free energies and equilibrium constants, variation of state functions as a function of T and P, 3^rd law.

Foundations of physical chemistry II (Spring semester)

Kinetic theory of gases: Pressure of a gas, Maxwell Boltzmann velocity and speed distribution, Collisions, Real gases (critical temperature, van der Waals equation of state) transport properties (effusion, viscosity, diffusion).

Rate equations: Rate equations from collision theory, molecularity and order of reactions the integrated rate laws (zero, 1^st and 2^nd order), Arrhenius equation, activated complex theory.

An introduction to spectroscopy: Nature of light (wavelength, frequency and wavenumber)

Atomic spectroscopy: electronic spectrum of H atom, Bohr theory, atoms with many electrons.

Molecular rotations and vibrations: Molecular spectra (vibrational, rotational, translational), classification of molecules in rotational spectra (symmetric tops, spherical tops, asymmetric tops), anharmonicity effects, Raman effect.

Electronic transitions: photo-electron spectroscopy, absorption spectroscopy, Beer-Lambert Law.

Magnetic resonance: electrons and nuclei in a magnetic field (Zeeman effect), chemical shift and spin relaxation.

Elements of physical chemistry, P. Atkins, J. de Paula, 5^th Ed., Oxford University Press, 2009.  ISBN 978-0-19-922672-6

Physical chemistry, K. J. Laidler, J. H. Meiser, 3^rd Ed., Houghton Mifflin Co., 1999.  ISBN 0-395-91848-0

Foundations of physical chemistry, N. Lawrence, J. Wadhawan, R. Compton, Oxford Chemistry Primers, 1999.  ISBN 0-19-850462-4

Foundations of physics for chemists, G. A. D. Ritchie, D. S. Sivia, Oxford Chemistry Primers, 2000.  ISBN 0-19-850360-1

Introduction to quantum theory and atomic structure, P. A. Cox, Oxford Chemistry Primers, 1996.  ISBN 0-19-855916-X