Thermodynamics of Non-Equilibrium Processes for Chemists with a Particular Application to Catalysis book cover

Thermodynamics of Non-Equilibrium Processes for Chemists with a Particular Application to Catalysis

Thermodynamics of non-equilibrium processes is a comparatively new area of thermodynamics. Traditionally this discipline is taught only to chemistry students who have a very strong background in physics. The author of the present book has adapted his course of thermodynamics of non-equilibrium processes so that the subject can be treated in terms understandable to any chemist with a formal physicochemical education in the fields of classical thermodynamics of equilibrium processes and traditional chemical kinetics.

The discipline combines thermodynamics and chemical kinetics and is helpful to researchers engaged in studying complex chemical transformations, in particular, catalytic transformations. For example, important concepts for such studies are conditions of kinetic irreversibility of complex stepwise stoichiometric reactions, rate-determining and rate-limiting stages, etc. In traditional chemical kinetics, these concepts are not very clear and tend to be “concealed” in courses. Fortunately, these concepts appear to be consistently and properly defined in terms of thermodynamics of non-equilibrium processes.

The present book is the synopsis of lectures on thermodynamics of non-equilibrium processes and a particular course on thermodynamics of operating catalysts.


Undergraduate and PhD students in chemical, chemical engineering or biological departments and researchers engaged in chemical kinetics, catalysis, chemical engineering and biophysics

Hardbound, 340 Pages

Published: October 2009

Imprint: Elsevier

ISBN: 978-0-444-53028-8


  • Chapter 1. Description of systems in thermodynamics of non-equilibrium processes

    § 1.1. Definitions

    § 1.2. The Second Law of thermodynamics as applied to open systems

    1.2.1. Entropy change in an open system

    1.2.2. Non-equilibrium systems with uniform and time-constant temperature and pressure. The quantity of diS for a homogeneous system in the presence of chemical transformations

    1.2.3. Fluxes of thermodynamic parameters; thermodynamic forces

    1.2.4. Thermodynamic conjugation of processes

    § 1.3. Fluxes and thermodynamic forces in spatially homogeneous chemically reactive systems

    1.3.1. The ‘thermodynamic’ form of kinetic equations

    1.3.2. Relationship between stationary rate and thermodynamic forces of a stepwise stoichiometric process which is a combination of elementary monomolecular reactions

    1.3.3. The hierarchy of the chemical potentials values intermediates at the stationary occurrence of stepwise processes

    § 1.4. The kinetic-thermodynamic analysis of the stationary mode of non-catalytic stepwise reactions

    1.4.1. Independence of the stationary rate of non-catalytic reaction of the standard values of thermodynamic parameters of the reactionintermediates

    1.4.2. Criteria of kinetic irreversibility of chemical reactions

    1.4.3. Rate-limiting, rate-determining and rate-controlling steps of a stationary stepwise reaction. Rate-determining parameters

    1.4.4. Rate-determining parameters of a sequence of monomolecular reactions

    1.4.5. Apparent activation energy of a stepwise process

    1.4.6. Rate-limiting steps, rate-determining parameters and apparent activation energy of simple schemes of chemical transformations

    1.4.7. Examples of a qualitative analysis of some peculiarities of stationary states of stepwise processes

    § 1.5. Thermodynamic forces in spatially non-uniform systems

    1.5.1. Calculation of thermodynamic forces in spatially non-uniform systems

    1.5.2. Examples of calculating the thermodynamic forces in spatially inhomogeneous systems

    § 1.6. Questions and problems for individual work

    Chapter 2. Thermodynamics of systems close to equilibrium (Non-equilibrium linear thermodynamics)

    § 2.1. Relationship between the values of flux and thermodynamic force close to thermodynamic equilibrium

    § 2.2. Interaction of thermodynamic processes and linear Onsager relations

    § 2.3. Examples of thermodynamic conjugation of the processes. Thermodynamic conjugation of stepwise chemical processes

    2.3.1. Transport of matter through a membrane in the presence of osmosis

    2.3.2. Active transport of matter through a membrane

    2.3.3. Examples of conjugate processes in spatially inhomogeneous systems

    2.3.4. Thermodynamic conjugation of cocurrent chemical reactions. Modified Onsager equations for conjugate chemical transformations far from equilibrium

    2.3.5. Examples of the Onsager reciprocal relations for the particular cocurrent stepwise processes with common intermediates

    § 2.4. Thermodynamic criteria of achievement and stability of stationary states

    2.4.1. The Prigozhin criterion (theorem) of the evolution for systems close to their thermodynamic equilibrium

    2.4.2. Stability of stationary state nearby equilibrium

    § 2.5. Thermodynamics of metabolic cycles and the direction of the evolution of living systems

    § 2.6. Questions and problems for individual work

    Chapter 3. Thermodynamics of systems far from equilibrium (Nonlinear nonequilibrium thermodynamics)

    § 3.1. Thermodynamic and kinetic approaches to description of system evolution far from equilibrium. Self-organization of matter far from thermodynamic equilibrium

    § 3.2. Criteria of evolution in nonlinear thermodynamics. The Glensdorf-Prigozhin universal criterion of evolution

    § 3.3. Thermodynamic criteria of the stability of stationary states far from equilibrium

    § 3.4. Reactive systems far from thermodynamic equilibrium

    3.4.1. Stationary state functionals (the Lyapunov functions) of reactive systems far from equilibrium

    3.4.2. Examples of the Lyapunov’s functions for simple kinetic schemes

    § 3.5. Thermodynamics and stability of nonlinear kinetic systems. Bifurcation points, diversity of stationary states and emergence of dissipative structures

    3.5.1. One-parameter system

    3.5.2. Schemes of the transformations with several intermediates. Stability of kinetic schemes according to Lyapunov

    § 3.6. Physicochemical behavior of dissipative structures

    3.6.1. Spatial dissipative structures. Bernard cells

    § 3.7. Questions and problems for individual work

    Chapter 4. Catalytic processes and thermodynamics of operating catalyst

    § 4.1. Operating catalysts as objects of the thermodynamics

    § 4.2. "Microkinetic" description of stationary catalytic reactions

    4.2.1. Some specific features of stationary catalytic reactions

    4.2.2. Stationary microkinetics and rate-determining parameters of the simplest intermediate-linear catalytic reactions

    4.2.3. Stationary microkinietics of simplest catalytic reactions which are nonlinear in respect of catalytic intermediates

    § 4.3. Stability of the stationary state of the operating catalyst

    4.3.1. The Lyapunov function for catalytic transformations which are linear in respect of catalytic intermediates

    4.3.2. Stability of the catalyst stationary state in the case of transformations nonlinear in respect of catalytic intermediates

    4.4. Energy correlations in catalysis

    4.4.1. Relationship between energy parameters of intermediates and the rate of the catalytic process

    4.4.2. Energy correlations and conditions of maximal activity of the catalyst reaction center

    4.4.3. The effect of the active component size on the rate of catalytic reactions

    § 4.5. Conjugation of catalytic processes. Relationship between thermodynamics and selectivity of catalytic processes

    4.5.1. The Horiuti-Boreskov-Onsager relations for parallel catalytic reactions with common intermediates

    4.5.2. Application of the Horiuti-Boreskov-Onsager equations for identifying the conditions of reversal of a catalytic transformation

    4.5.4. Conclusions

    § 4.6. Specific properties of the non-equilibrium state of operating catalysts. Dissipative structures in catalysis

    4.6.1. Specific features of non-equilibrium stable states of the operating catalyst

    4.6.2. Temporal and spatio-temporal dissipative structures in catalytic systems

    § 4.7. Questions for individual work

    Chapter 5. Application of non-equilibrium thermodynamics to material science

    § 5.1. Some features of thermodynamics of material synthesis

    § 5.2. Synthesis of thermodynamically unstable compounds and materials

    § 5.3. The Ostwald step rule for the phase transformations

    § 5.4. Synthesis of carbon nanofilaments, nanofibers and nanotubes

    § 5.5. Questions and problems for individual work

    Chapter 6. Entropy and information

    § 6.1. Timing hierarchy of processes in complex dynamic systems. Quasi-stationary subsystems

    § 6.2. Relationship between entropy and dynamic stability of a system

    § 6.3. Relationship between entropy and information

    § 6.4. The quantity of biological information

    § 6.5. The value of information

    § 6.6. Reception and expression of information in dynamic systems

    § 6.7. Bioinformatics and its application to biology and biochemistry

    § 6.8. Questions and problems for individual work


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