Module Details

The information contained in this module specification was correct at the time of publication but may be subject to change, either during the session because of unforeseen circumstances, or following review of the module at the end of the session. Queries about the module should be directed to the member of staff with responsibility for the module.
Title Physical Chemistry II
Code CHEM260
Coordinator Dr GR Darling
Chemistry
Darling@liverpool.ac.uk
Year CATS Level Semester CATS Value
Session 2021-22 Level 5 FHEQ Whole Session 15

Pre-requisites before taking this module (or general academic requirements):

CHEM152 CHEM152 Introductory Physical Chemistry; CHEM170 Introductory Spectroscopy 

Aims

• 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 introduction into basic concepts of quantum mechanics.
• To advance knowledge of quantitative analysis of molecular spectra.
• To make students familiar with the basic ideas of photochemistry.


Learning Outcomes

(LO1) Demonstrate an understanding of the laws of thermodynamics and how they can be applied to thermochemical calculations

(LO2) Show ability to employ the methods of chemical kinetics to describe and analyse the time-dependence of chemical processes.

(LO3) Demonstrate an understanding of the basic concepts of quantum mechanics, including operators and wavefunctions, and their application to simple systems.

(LO4) Show an understanding of different types of molecular energy levels, the forms of spectroscopy which involve transitions between them, and how molecular quantities can be extracted from the spectra.

(S1) Critical thinking and problem solving - Evaluation

(S2) Critical thinking and problem solving - Problem identification

(S3) Numeracy/computational skills - Reason with numbers/mathematical concepts

(S4) Numeracy/computational skills - Confidence/competence in measuring and using numbers

(S5) Numeracy/computational skills - Problem solving


Teaching and Learning Strategies

This module consists of 38 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 eight 1.5 hour workshops given over the two semesters at times to be published.


Syllabus

 

Thermodynamics

1. Revision of material in Chem152: Ideal gas equation, standard states, first law of thermodynamics, heat & work, enthalpy, Hess' law cycles, entropy, Gibbs energy, equilibrium constant. Examples of calculations using tables of thermodynamic data.
2. Heat capacity at constant volume or pressure, temperature dependence of internal energy and enthalpy.
3. Second law of thermodynamics, statistical description of entropy. Dependence of entropy on temperature and pressure, third law of thermodynamics.
4. Gibbs free energy, changes at constant temperature or pressure. Equilibrium constant K, relation to Gibbs free energy, variation with temperature and pressure, relation to mole fraction.
5. Chemical potential, equilibrium and the extent of reaction. Effect of temperature and pressure on equilibria. Extension from gas phase reactions to all reactions.
6. Real gases, deviations from ideal behaviour, virial and van der Waals equations of state.
7. Ideal liquids and solutions. Raoult's law. The chemical potential of components in ideal mixtures: standard and reference states. Colligative properties. Deviations from ideality.
8. Phase transition of pure substances and mixtures; enthalpy and entropy change upon phase transition; phase diagrams.

Kinetics

1. Revision of material in Chem152: Chemical reaction rates, rate equation, reaction orders, integrated rate equations, half-life, activation energy barriers and Arrhenius equation.
2. Derivation of zero-, first- and second order integrated rate eqns. Determination of reaction order and rate constant: straight plots. Half-life time of a reaction.
3. Kinetic gas model, collision rates. Simple collision theory (SCT). Potential energy barriers. Reactive Encounters. Comparison of SCT with experimental results. Steric hindrance. Transition state. TransitionState Theory.
4. Consecutive reac tions. The rate determining step.
5. Parallel reactions. Reverse reaction and relaxation towards equilibrium.
6. Pre-equilibrium; steady state approximation. Diffusion-controlled reactions.
7. Michaelis-Menten Mechanism. Lindemann-Hinshelwood mechanism. Chain reactions.
8. Kinetics of excited state decay, quantum yield, fluorescence quenching, photochemical reactions

Quantum mechanics

1. Basic postulates of quantum mechanics and their interpretation, including: wave-functions and Born interpretation and Heisenberg uncertainty relations.
2. Methods of quantum mechanics including: properties of operators and the relationship to physical observables, eigenvalue equations and expectation values, transition dipole moments.
3. Hamiltonian and momentum operators, the basics of the Schrödinger equation.
4. Examples of the Schrödinger equation, including: particle in a one-dimensional box, particle on a ring, t unnelling, atomic and molecular energy levels, potential energy curves, the Born-Oppenheimer Approximation.
5. Bonding in simple molecules.

Spectroscopy

1. The basics of spectra formation: transitions, energy scales, line widths.
2. Rotation spectra of diatomics: eigenvalues, selection rules, line spacing, quantitative description.
3. Harmonic oscillator model of molecular vibrations: eigenvalues, selection rules.
4. The rotation-vibrations spectrum: qualitative appearance, line spacings in the harmonic oscillator rigid rotor approximation, quantitative description.
5. Anharmonicity: comparison to harmonic oscillator, effects on IR spectra.
6. Vibrations of polyatomics (revision).
7. Electronic transitions: the Franck-Condon Principle, selection rules, vertical transitions, vibrational structure.

Photochemistry

1. Dissociation induced by electronic transitions: Bound - bound and bound - free (continuum) transitions.
2. Jablonski diagram, radiative and non-radiative decay processes, fluorescence and phosphorescence.


Recommended Texts

Reading lists are managed at readinglists.liverpool.ac.uk. Click here to access the reading lists for this module.

Teaching Schedule

  Lectures Seminars Tutorials Lab Practicals Fieldwork Placement Other TOTAL
Study Hours 40

  8

      48
Timetable (if known)              
Private Study 102
TOTAL HOURS 150

Assessment

EXAM Duration Timing
(Semester)
% of
final
mark
Resit/resubmission
opportunity
Penalty for late
submission
Notes
formal examination  180 minutes    80       
3x 2 hour remote tests, answers to be submitted electronically.  each class test is 1    20       
CONTINUOUS Duration Timing
(Semester)
% of
final
mark
Resit/resubmission
opportunity
Penalty for late
submission
Notes