Generalized van der Waals Theory of Molecular Fluids in Bulk and at Surfaces

Generalized van der Waals Theory of Molecular Fluids in Bulk and at Surfaces

1st Edition - September 5, 2018

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  • Authors: Sture Nordholm, Jan Forsman, Cliff Woodward, Ben Freasier, Zareen Abbas, Robert Penfold
  • Paperback ISBN: 9780128111369
  • eBook ISBN: 9780128111901

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Generalized van der Waals Theory of Molecular Fluids in Bulk and at Surfaces presents successful research on the development of a new density theory of fluids that makes it possible to understand and predict a wide range of properties and phenomena. The book brings together recent advances relating to the Generalized van der Waals Theory and its use in fluid property calculations. The mathematics presentation is oriented to an audience of varying backgrounds, and readers will find exercises that can be used as a textbook for a course at the upper undergraduate or graduate level in physics or chemistry. In addition, it is ideal for scientists from other areas, such as geophysics, oceanography and molecular biology who are interested in learning about, and understanding, molecular fluids.

Key Features

  • Presents an approximate, but fully derived and physically explained, theory of molecular fluids to facilitate broad applications
  • Derives a density functional theory of classical fluids and applies it to obtain equations of state, as well as non-uniform fluid properties, e.g., surface tension and adsorption
  • Demonstrates how the theory can be applied to complex multi-center molecules forming a polymer fluid
  • Provides user-friendly programs to redraw figures for variable parameters and to perform calculations in particular applications
  • Includes a set of exercises to support use of the book in a course


Researchers in statistical mechanics, scientists and engineers working with fluids as well as graduate and upper undergraduate students in chemistry, chemical engineering and physics

Table of Contents

  • 1 Introduction

    2 Foundations

    3 Ideal Molecular Gases

    3.1 Equation of state

    3.2 Thermochemistry

    4 Intermolecular Potentials

    4.1 Simple fluids - Generic potentials

    4.2 Electrostatic interactions in molecular fluids

    4.3 Effective electrostatic interactions

    4.4 Distributed interactions

    5 Basic Equations of State for Simple Fluids

    5.1 The virial equation of state

    5.2 The van der Waals equation of state

    5.3 The phase diagram of a fluid

    5.4 Empirical equations of state

    6 The Generalized van der Waals Theory

    6.1 The free energy density functional theory

    6.1.1 The local functional

    6.1.2 The nonlocal functional

    6.2 The GvdW theory of simple fluid equations of state

    6.2.1 Hard spheres

    6.2.2 Lennard-Jones fluids

    6.2.3 Quantum effects on simple fluid equations of state

    7 Simple Fluid Mixtures

    7.1 Ideal gas mixtures

    7.2 Interacting simple fluid mixtures

    7.2.1 Interactions in mixtures

    7.2.2 Excess properties of mixtures

    7.2.3 Regular solution theory

    7.2.4 One-fluid theory

    7.2.5 GvdW theory

    8 Surface Tension in Simple Fluids

    8.1 Mechanical definition of surface tension

    8.2 GvdW free energy theory of surface tension

    8.2.1 Simple step function profile and local entropy theory

    8.2.2 Improved estimates of surface tension

    8.2.3 Interfacial tension in fluid mixtures

    8.2.4 Classical theory of nucleation

    8.2.5 Curvature dependence of surface tension

    8.2.6 Drop or bubble stability - The Young-Laplace relation

    9 Adsorption at Solid Surfaces

    9.1 The simplest isotherm of adsorption - Henry's Law

    9.2 The Langmuir adsorption isotherm

    9.3 GvdW theory of single layer adsorption

    9.4 Multilayer adsorption

    9.4.1 The BET theory

    9.4.2 GvdW theory of adsorption

    10 Electrolyte fluids

    10.1 Screening and thermodynamics of salt solutions

    10.2 Ionic liquids

    11 Polymer Fluids

    11.1 Lattice theory according to Flory-Huggins

    11.2 Polymer extension of GvdW theory

    12 Summary and Outlook

Product details

  • No. of pages: 380
  • Language: English
  • Copyright: © Elsevier 2018
  • Published: September 5, 2018
  • Imprint: Elsevier
  • Paperback ISBN: 9780128111369
  • eBook ISBN: 9780128111901

About the Authors

Sture Nordholm

Dr. Sture Nordholm did his research training in statistical mechanics with Robert Zwanzig and continued with postdoctoral research at The University of Chicago with Stuart Rice. His doctoral thesis was on nonequilibrium transport theory and he continued in Chicago working on both fundamental problems in molecular dynamics and theory of liquids. His career then took him to The University of Sydney and finally to The University of Gothenburg. Over his career he has acquired research experience in a broad area of theoretical physical chemistry including reaction rate theory, density functional theory of fluids (both classical and quantum mechanical) and theory of chemical bonding. His publication list includes over 200 articles and a book.

Affiliations and Expertise

Professor Emeritus, Chemistry, The University of Gothenburg, Sweden

Jan Forsman

Dr. Jan Forsman did his research training at The University of Lund where he worked on interactions between colloidal particles in dispersions and between ions and charged surfaces in electrolyte solutions. After obtaining his PhD in 1998 he took a position in chemical industry (Chemitec, Perstorp AB) in Sweden but returned to academia after a couple of years. He was a postdoc with Clifford Woodward in Canberra and then returned to The University of Lund where he established himself as a leading expert on both Monte Carlo simulation and density functional theory of molecular fluids including polymer fluids and ionic liquids. He has authored more than 80 research articles.

Affiliations and Expertise

Theoretical Chemistry, Lund University, Sweden

Cliff Woodward

Dr. Clifford Woodward studied at The University of Sydney where he obtained his PhD in Theoretical Chemistry in 1985. His research was focused on the development of the GvdW theory of fluids to account for interactions between polar molecules. He moved on to do research as a postdoc and Research Fellow at The University of Lund in Sweden where, over a five year period, he extended his work into colloidal systems, electrolyte solutions and, particularly, polymer fluids. Currently, he is an Associate Professor at The University of New South Wales, Canberra. His research is in the area of condensed matter physics, including polymer fluids, ionic liquids and cell membrane interactions. In particular, he has made major contributions to the theory of non-uniform polymer fluids and is author of more than 120 articles.

Affiliations and Expertise

Professor, ADFA, University of NSW, Canberra, ACT, Australia

Ben Freasier

Dr. Ben Freasier did his research training with K. Runnels at Louisiana State University where he got his PhD in statistical mechanics of lattice models of fluids and interfaces in 1973. He was hired to assist in the setting up of a research group in statistical mechanics at The Royal Military College Duntroon in Canberra which later became the ADFA campus of The University of New South Wales. His research was focused on integral equation theory and simulation of fluids and included early simulations of collisional energy transfer in liquids and novel microcanonical sampling methods. He also has been active in the programming of educational software and commercial computer games and as a general programming consultant. He is a passionate user and occasional lecturer and instructor in the use of the Python programming language. He has published more than 100 research articles.

Affiliations and Expertise

Programming Consultant, Canberra, ACT, Australia

Zareen Abbas

Dr. Zareen Abbas has a PhD in inorganic chemistry from The University of Gothenburg and spent one year as postdoc at The University of Innsbruck, Austria. He has played a major role in the development and implementation of the Corrected Debye-Hückel (CDH) theory of salt solutions and surface complexation. The CDH theory is based on the GvdW density functional theory and permits ion size effects to be semianalytically estimated. He has applied this theory extensively to model activity and osmotic coefficients of simple and mixed electrolytes exploring the generally good accuracy in comparisons with experimental and Monte Carlo simulation data. Recently he has further developed the theory to predict the surface charging of nanoparticles. He has demonstrated that the CDH theory is capable of very accurately resolving the observed size dependency of the particle charge in the case of surfaces composed of SiO2, TiO2 or iron oxides.

Affiliations and Expertise

Lecturer, Chemistry, The University of Gothenburg, Sweden

Robert Penfold

Dr. Robert Penfold did his research training at The University of Gothenburg, Sweden, where he worked on the development of the GvdW density functional theory for use on electrolyte solutions. He received his PhD in 1993 and then did postdoctoral research at The University of Lund in the theory of fluids combining numerical and analytical mathematical methods in the prediction of physical properties. He subsequently moved to England where he combines part time instruction at The Open University with full time research at The Institute of Food Research in Norwich, East Anglia.

Affiliations and Expertise

Senior Staff Researcher, The Institute of Food Research, Norwich, UK

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