Elective Module:

CE4-33 Molecular Modelling of Fluids

Molecular Modelling of Fluids Introduction – Slide 1 © Imperial College London

 Lecturers

Amparo Galindo
Andrew J. Haslam

George Jackson

Molecular Modelling of Fluids Introduction – Slide 2 © Imperial College London

 Molecular Systems Engineering Group

http://molecularsystemsengineering.org/

Molecular Modelling of Fluids Introduction – Slide 3 © Imperial College London

 Molecular-Level Process Engineering
Process model
building
Process
Molecular simulation
simulation

Process and Process

optimisation
Molecular theory and
model building molecular models
SAFT
Molecular
design

Physical
property Integrated process and
prediction product design

Molecular Modelling of Fluids Introduction – Slide 4 © Imperial College London

 CE4-33 Course Syllabus

Molecular Modelling of Fluids Introduction – Slide 5 © Imperial College London

 CE4-33 Course Syllabus

The goal of this course is to provide students with the

background and skills needed to appreciate and understand
the application of molecular theory and simulation in
modelling fluids and fluid mixtures.

Some of the theoretical fundamentals (statistical

thermodynamics, distribution functions, perturbation
theories) and modern computational methods (Monte Carlo
and molecular dynamics) will be developed in lectures and
applied in a number of interactive classes and min projects to
be carried out during the timetabled sessions.

Molecular Modelling of Fluids Introduction – Slide 6 © Imperial College London

 CE4-33 Course Syllabus

The specific objectives of the course include:

• An understanding of the basis of statistical thermodynamics
as applied to fluid systems.
• The development of the statistical associating fluid theory
(SAFT) as an advanced molecular-based equation of state
for the thermodynamic properties of complex fluid mixtures.
• An understanding of the modelling of fluid phase equilibria
of mixtures with equations of state.
• An exploration of the role of modern molecular-simulation
techniques in modelling the thermodynamic, structural and
dynamical properties of fluids

Molecular Modelling of Fluids Introduction – Slide 7 © Imperial College London

 CE4-33 Course Syllabus

Course Outline (6 Themes in 10 Sessions)

Session 1 Introduction to Statistical Thermodynamics (AJH):
• Statistical interpretation of entropy;
• Boltzmann distribution and the partition function;
• Ensembles and the canonical distribution;
• Link to macroscopic thermodynamics.
Sessions 2 & 3 Theory of the Liquid State (AJH):
• Density and distribution functions;
• Thermodynamic properties and the radial distribution function;
• Perturbation theories of liquids;
• Ideal gases and van der Waals (VDW) equation of state from
statistical thermodynamics.
Molecular Modelling of Fluids Introduction – Slide 8 © Imperial College London
 CE4-33 Course Syllabus

Sessions 4 & 5 Engineering Equations of State (AJH/GJ):

• van der Waals equation of state and corresponding states;
• Other cubic equations of state (RK, SRK etc.);
• The statistical associating fluid theory (SAFT);
• Applications of SAFT to modelling the
thermodynamic properties of fluids.
Sessions 6 & 7 Modelling Fluid-Phase Equilibria of Mixtures (AG):
• Fluid phase behaviour and phase diagrams;
• Phase behaviour in mixtures including vapour-liquid (VLE)
liquid-liquid (LLE), vapour-liquid-liquid (VLLE) equilibria etc.;
• Extending equations of state to modelling mixtures with
mixing rules and unlike parameters;
• Calculation the fluid phase equilibria (ASPEN).
Molecular Modelling of Fluids Introduction – Slide 9 © Imperial College London
 CE4-33 Course Syllabus

Sessions 8 & 9 Molecular Simulation Approaches (GJ):

• Atomistic simulations using molecular force fields;
• The basis of Monte Carlo (MC) simulation;
• The basis of molecular dynamics (MD) simulation;
• Using molecular simulation to compute the thermophysical
properties of fluids and fluid mixtures;
Session 10 Industrial Applications (Guest Lecturer):
• What contributions can equations of state and
molecular simulation make in industry?
• Future challenges and opportunities.

Molecular Modelling of Fluids Introduction – Slide 10 © Imperial College London

 CE4-33 Course Syllabus

Sessions will include:

• 4 “Interactive Classes” for hands on problem solving
as a group;
• 3 “Mini Projects” to work through individually and
hand in for assessment the following week;
• The Mini Projects will be assessed and will contribute
20% of the overall course grade.
Lecture Schedule (Tentative):
• See CE4-33 Molecular Modelling of Fluids (2016-2017) tab
on Blackboard
https://bb.imperial.ac.uk/

Molecular Modelling of Fluids Introduction – Slide 11 © Imperial College London

 Further Reading

• Lecture Notes
A. J. Haslam (Imperial College London, 2016)
• Statistical Thermodynamics
T. L. Hill, An Introduction to Statistical Thermodynamics (Dover, 2003)
J. S. Rowlinson, Evolution of Statistical Mechanical Ideas, Molecular Physics, 104, 3399 (2006)
• Theory of Liquid State
J.-P. Hansen & I. R. McDonald, Theory of Simple Liquids, 3rd Edition (Academic Press, 2006)
C. J. Gray & K. E. Gubbins, Theory of Molecular Fluids, Volumes I & 2 (Oxford University Press,
1984 & 2011)
• Phase Equilibria of Mixtures
P. Atkins & J. de Paula, Physical Chemistry, 9th Edition (Oxford University Press, 2009)
J. S. Rowlinson and F. L. Swinton, Liquids and Liquid Mixtures (Butterworth Scientific, 1982)
• Molecular Simulation
M. P. Allen & D. J. Tildesley, Computer Simulation of Liquids (Oxford University Press, 1987)
D. Frenkel & B. Smit, Understanding Molecular Simulation, 2nd Edition (Academic Press, 2002)

Molecular Modelling of Fluids Introduction – Slide 12 © Imperial College London

 Mini Project 2

• Sessions 6 (17/11) and 7 (24/11) will require

the use of ASPEN during the class
– Go to https://softwarehub.imperial.ac.uk/
– Install Aspen v8.4 in your laptops
– Please check before Session 6 that you can run Aspen
on your computer
– Bring laptops fully charged to class

Molecular Modelling of Fluids Introduction – Slide 13 © Imperial College London