CHEM2301: Physical Chemistry

Course Organizer: Dr Simon T. Banks

Lecturers: Dr K Holt, Dr D J Caruana, Dr Simon T. Banks, Prof N Kaltsoyannis, Dr D M Rowley

Normal prerequisite: CHEM1301

Units: 1


The aims of this course are to develop further quantum mechanics and thermodynamics and to extend the material of CHEM1301 to spectroscopy, kinetics, and electrochemistry.


Students will be able to

  • apply the fundamental postulates of quantum mechanics to problems with exact and approximate solutions
  • use molecular orbital theory with diatomic molecules and Hückel theory with p electron systems
  • apply the second law of thermodynamics to homogeneous and heterogeneous systems
  • apply thermodynamics to phase equilibria and chemical equilibria
  • understand electrochemical systems in terms of simple electroyte theory
  • use the stationary state approximation to study unimolecular, linear and branched chain reactions
  • analyse chemical systems using atomic, rotational, vibrational and electronic spectroscopy
  • discuss the fates of electronically excited molecules

Course Structure

  • Lectures: 45
  • Tutorials: 20
  • Labs: 5 afternoons


  • Exam: 70% (3 hours)
  • Lab: 20%
  • Coursework: 10%

Practical course organizer:

Dr S T Banks

Recommended Texts

  • R Silbey, R A Alberty and M G Bawendi Physical Chemistry 4th Edition John Wiley. Earlier editions of Ailbey and Alberty are equally useful.

An acceptable alternative is:

  • P W Atkins and J de Paula Atkins' Physical Chemistry 8th edition, Oxford 2006; or earlier editions

Further Reading

  • M L McGlashan, "Chemical Thermodynamics", 2nd ed, Academic Press
  • I N Levine, "Quantum Chemistry", 4th ed, Prentice Hall, 1991
  • J M Hollas, Modern Spectroscopy", 2nd ed, Wiley, 1992
  • A Gilbert and J Baggott, "Essentials of Molecular Photochemistry", Blackwells,1991

Course Outline

Quantum Mechanics NK, 9 lectures

  • Fundamental principles and postulates: probability interpretation of Ψ, operators and Hamiltonians, eigenvalue equations, Schrödinger equation, expectation values, Variation principle, more dimensions and particles.
  • Exact solutions to the Schrödinger equation: harmonic oscillator, particle on a ring, particle on a sphere (rigid rotor), hydrogen atom.
  • Beyond exact solutions: helium atom.
  • Molecular orbitals: Born-Oppenheimer approximation, linear combination of atomic orbitals, secular equations, two-orbital systems.
  • Hückel theory for π‑electron systems.

Thermodynamics STB, 9 lectures

  • The second law of thermodynamics is introduced and its application to chemical systems is developed.
  • Equilibrium: thermal, hydrostatic, diffusive, and chemical.
  • Revision of the first law from CHEM1301: calorimetry; flow calorimetry of gases; isothermal and isenthalpic Joule Thomson coefficients and heat capacity.
  • Partial differentiation; importance of T and p , as variables.
  • Equalities of the second law of thermodynamics; thermodynamic surfaces; Gibbs and Helmholtz energies; entropy, Maxwell equations; variation of T and p ; Gibbs-Helmholtz equation; van't Hoff equation; integrated second-law equations; Gibbs-Duhem equation.
  • Homogeneous systems: use of integrals to determine the change in state of a phase. Gas expansions: isenthalpic and isentropic; liquefaction of gases;differences in heat capacities and compressibilities; the speed of sound.
  • Heterogeneous systems: densities and fields; applications of the Gibbs-Duhem equation; phase equilibrium; vapour pressure and the Clapeyron equation, Trouton's rule.
  • Tabulated thermodynamic data, calculation of equilibrium constants.

Kinetics, Photochemistry and Atmospheric Chemistry DMR, 9 lectures

  • Gas-phase kinetics: stationary state approximation; unimolecular reactions; Lindemann mechanism; introduction to RRKM theory.
  • Linear chain reactions: classification of elementary steps; pyrolysis of ethanal and ethane.
  • Excitation and the fate of electronically excited states of molecules; fluorescence, phosphorescence, non-radiative processes, vibrational relaxation, Stokes shift, dissociation, predissociation, quenching.

Spectroscopy KH, 9 lectures

  • Atomic Spectroscopy: The H atom, term symbols, selection rules, absorption and emission spectra for Na, the Helium atom, spectra of many electron atoms.
  • Molecular Spectroscopy: Born-Oppenheimer approximation, experimental techniques, rotational spectroscopy: selection rules, energy level expressions, intensities, centrifugal distortion, deriving bond lengths.
  • Vibrational Spectroscopy: harmonic and anharmonic oscillators, selection rules, force constants, vibration-rotation spectra, dissociation energies, hot bands.

Solutions and Electrolyte Solutions DJC, 9 lectures

  • Ideal solutions, non-ideal solutions. Henry's law and Raoult's law. Coligative properties in general. Electrolyte solutions. Columbic interactions, deviations from ideal behaviour.
  • Debye Hiickel model for electrolyte solutions of Derivation of limiting law. Conductivity of electrolye solutions. Molar conductivity, strong and weak electrolytes. Onsanger equation. Kohlrausch's Law, Grotthus mechanism. Transport numbers.
  • Electrochemical potential. Electrochemical cells. Standard electrode reactions. The standard hydrogen electrode. Nernst equation. Electrochemical redox reactions, Half cell reactions. Overall cell reactions. Measurement of emf. Cell potential convention.
  • Thermodynamics of electrode/solution interface. Conventional representation of electrochemical cells. Liquid Junctions and salt bridges. Electrochemical double layer parallels with the Debye Hiickel model. Electrode reactions.