- To appreciate how how the behaviour of atoms, molecules and energy levels gives rise to useful thermodynamic principles, such as Gibbs energy and equilibrium constants.
- To understand that ΔG is a useful indicator of the direction of change, and to be able to calculate ΔG for a variety of different chemical systems and conditions.
- To understand the differences between ideal and non-ideal mixing, and to show that ideal mixing is driven only by entropy.
- To understand the concept of chemical potential and its predictive ability for chemical change.
- To understand how equilibria arise, and the response of equilibria to changes in process conditions.
- To realise that equilibria can also be calculated from first principles, by considering the partition functions of the reactants and products.
||This course of 6 lectures follows on directly from the course on Molecular Thermodynamics. The aim is to build on the concepts in this previous course, and to develop the concepts of chemical thermodynamics for interacting systems. The course will be taught using an approach which considers how the behaviour of atoms, molecules and energy levels gives rise to useful thermodynamic principles, such as Gibbs energy and equilibrium constants.
1 workshop (1 hour) accompanies the course. There will also be a linking workshop which covers some of the material common to this course and the previous one on Molecular Thermodynamics. Online questions will be available to give you examples of possible exam questions.
- Reversible systems, Trouton’s law & exceptions, Irreversible changes, ΔG as the indicator of direction of change, Lattice model example, ΔG as a function of temperature (Gibbs-Helmholtz Eqn).
- ΔG as a function of pressure for liquids/solids and gases, chemical potential, using ΔG to predict phase changes, phase boundaries, Clapeyron Eqn, Clausius-Clapeyron Eqn, simple phase diagrams.
- Mixtures – variation of ΔG with composition, partial molar quantities & chemical potential, the Fundamental Equation, equations for ΔG, ΔH and ΔS of mixing ideal gases derived from a (a) statistical method, (b) standard method, and (c) molecular interpretation.
- Ideal liquid mixtures and solutions, brief look at real solutions, chemical potentials in a mixture, Raoult’s Law, Henry’s Law, how concentration affects melting/boiling points of solutions, dissociation of salts in solution, degree of dissociation.
- Relationship between ΔG and equilibria, perfect gas equilibria, general reaction equilibria, response of equilibria to temperature & pressure, Le Chatelier’s principle, the van’t Hoff Eqn.
- Statistical description of equilibria, relating K to the partition functions of reactants & products for (a) exothermic, (b) endothermic reactions, (c) endothermic reactions where product has high d.o.s., a worked example of how to calculate K from q.
- Molecular Driving Forces, 2nd Edition, KA Dill and S Bromberg, Garland, 2011
- Quanta, Matter, and Change, P W Atkins, J de Paula and R Friedman, Oxford, 2009