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Preface of the second edition

Preface of the first edition

1Scope

1.1What is non-equilibrium thermodynamics?

1.2Non-equilibrium thermodynamics in the context of other theories

1.3Purpose of this book

2Why non-equilibrium thermodynamics?

2.1Simple flux equations

2.2Flux equations with coupling terms

2.3Experimental designs and controls

2.4Entropy production, work and lost work

2.5Consistent thermodynamic models

3Thermodynamic relations for heterogeneous systems

3.1Two homogeneous phases separated by a surface in global equilibrium

3.2The contact line in global equilibrium

3.3Defining thermodynamic variables for the surface

3.4Local thermodynamic identities

3.5Defining local equilibrium

3.AAppendix: Partial molar properties

3.A.1Homogeneous phases

3.A.2The surface

3.A.3Standard states

4The entropy production for a homogeneous phase

4.1Balance equations

4.2The entropy production

4.2.1Why one should not use the dissipation function

4.2.2States with minimum entropy production

4.3Examples

4.4Frames of reference for fluxes in homogeneous systems

4.4.1Definitions of frames of reference

4.4.2Transformations between the frames of reference

4.AAppendix: The first law and the heat flux

5The excess entropy production for the surface

5.1The discrete nature of the surface

5.2The behavior of the electric fields and the potential through the surface

5.3Balance equations

5.4The excess entropy production

5.4.1Reversible processes at the interface and the Nernst equation

5.4.2The surface potential jump at the hydrogen electrode

5.5Examples

6The excess entropy production for a three-phase contact line

6.1The discrete nature of the contact line

6.2Balance equations

6.3The excess entropy production

6.4Stationary states

6.5Concluding comment

7Flux equations and Onsager relations

7.1Flux–force relations

7.2Onsager’s reciprocal relations

7.3Relaxation to equilibrium: Consequences of violating Onsager relations

7.4Force–flux relations

7.5Coefficient bounds

7.6The Curie principle applied to surfaces and contact lines

8Transport of heat and mass

8.1The homogeneous phases

8.2Coefficient values for homogeneous phases

8.3Thesurface

8.3.1Heats of transfer for the surface

8.4Solution for the heterogeneous system

8.5Scaling relations between surface and bulk resistivities

9Transport of heat and charge

9.1The homogeneous phases

9.2The surface

9.3Thermoelectric coolers

9.4Thermoelectric generators

9.5Solution for the heterogeneous system

10Transport of mass and charge

10.1The electrolyte

10.2The electrode surfaces

10.3Solution for the heterogeneous system

10.4A salt power plant

10.5Electric power from volume flow

10.6Ionic mobility model for the electrolyte

10.7Ionic and electronic model for the surface

11Evaporation and condensation

11.1Evaporation and condensation in a pure fluid

11.1.1The entropy production and the flux equations

11.1.2Interface resistivities from kinetic theory

11.2The sign of the heats of transfer of the surface

11.3Coefficients from molecular dynamics simulations

11.4Evaporation and condensation in a two-component fluid

11.4.1The entropy production and the flux equations

11.4.2Interface resistivities from kinetic theory

12Multi-component diffusion, heat conduction and cross effects

12.1The homogeneous phases

12.2The Maxwell–Stefan equations for multi-component diffusion

12.3The Maxwell–Stefan equations for the surface

12.4Multi-component diffusion

12.4.1Prigogine’s theorem

12.4.2Diffusion in the solvent frame of reference

12.4.3Other frames of reference

12.4.4An example: Kinetic demixing of oxides

12.5A relation between the heats of transfer and the enthalpy

13A non-isothermal concentration cell

13.1The homogeneous phases

13.1.1Entropy production and flux equations for the anode

13.1.2Position-dependent transport coefficients

13.1.3The profiles of the homogeneous anode

13.1.4Contributions from the cathode

13.1.5The electrolyte contribution

13.2Surface contributions

13.2.1The anode surface

13.2.2The cathode surface

13.3The thermoelectric potential

14The transported entropy

14.1The Seebeck coefficient of cell a

14.2The transported entropy of Pb²⁺ in cell a

14.3The transported entropy of the cation in cell b

14.4The transported entropy of the ions cell c

14.5Transformation properties

14.6Concluding comments

15Adiabatic electrode reactions

15.1The homogeneous phases

15.1.1The silver phases

15.1.2The silver chloride phases

15.1.3The electrolyte

15.2The interfaces

15.2.1The silver–silver chloride interfaces

15.2.2The silver chloride–electrolyte interfaces

15.3Temperature and electric potential profiles

16The liquid junction potential

16.1The flux equations for the electrolyte

16.2The liquid junction potential

16.3Liquid junction potential calculations compared

16.4Concluding comments

17The formation cell

17.1The isothermal cell

17.1.1The electromotive force

17.1.2The transference coefficient of the salt in the electrolyte

17.1.3An electrolyte with a salt concentration gradient

17.1.4The Planck potential derived from ionic fluxes and forces

17.2A non-isothermal cell with a non-uniform electrolyte

17.2.1The homogeneous anode phase

17.2.2The electrolyte

17.2.3The surface of the anode

17.2.4The homogeneous phases and the surface of the cathode

17.2.5The cell potential

17.3Concluding comments

18Power from regular and thermal osmosis

18.1The potential work of a salt power plant

18.2The membrane as a barrier to transport of heat and mass

18.3Membrane transport of heat and mass

18.4Osmosis

18.5Thermal osmosis

19Modeling the polymer electrolyte fuel cell

19.1The potential work of a fuel cell

19.2The cell and its five subsystems

19.3The electrode backing and the membrane

19.3.1The entropy production in the homogeneous phases

19.3.2The anode backing

19.3.3The membrane

19.3.4The cathode backing

19.4The electrode surfaces

19.4.1The anode catalyst surface

19.4.2The cathode catalyst surface

19.5A model in agreement with the second law

19.6Concluding comments

20Measuring membrane transport properties

20.1The membrane in equilibrium with electrolyte solutions

20.2The membrane resistivity

20.3Ionic transport numbers

20.4The transference number of water and the water permeability

20.5The Seebeck coefficient

20.6Interdiffusion coefficients

21The impedance of an electrode surface

21.1The hydrogen electrode: Mass balances

21.2The oscillating field

21.3Reaction Gibbs energies

21.4The electrode surface impedance

21.4.1The adsorption–diffusion layer in front of the catalyst

21.4.2The charge transfer reaction

21.4.3The impedance spectrum

21.5A test of the model

21.6The reaction over potential

22Non-equilibrium molecular dynamics simulations

22.1The system

22.1.1The interaction potential

22.2Calculation techniques

22.3Verifying the assumption of local equilibrium

22.3.1Local equilibrium in a homogeneous binary mixture

22.3.2Local equilibrium in a gas–liquid interface

22.4Verifications of the Onsager relations

22.4.1A homogeneous binary mixture

22.4.2Agas–liquidinterface

22.5Linearity of the flux–force relations

22.6Molecular mechanisms

23The non-equilibrium two-phase van der Waals model

23.1Van der Waals equation of states

23.2Van der Waals square gradient model for the interfacial region

23.3Balance equations

23.4The entropy production

23.5Flux equations

23.6A numerical solution method

23.7Procedure for extrapolation of bulk densities and fluxes

23.8Defining excess densities

23.9Thermodynamic properties of Gibbs’ surface

23.10An autonomous surface

23.11Excess densities depend on the choice of dividing surface

23.11.1Properties of dividing surfaces

23.11.2Surface excess densities for two dividing surfaces

23.11.3The surface temperature from excess density differences

23.12The entropy balance and the excess entropy production

23.13Resistivities to heat and mass transfer

23.14Concluding comments

24Curved surfaces

24.1Density profiles and the parameter m

24.2Balance equations

24.3The entropy production

24.4The surface resistivity to heat

24.5The curvature dependence of the resistivities

24.6Concluding remarks

25The catalyst surface temperature

25.1Heterogeneous catalysis

25.2The effect of coupling

25.3Surface temperature and Arrhenius plot

25.4Concluding remarks

Bibliography

Symbol lists

Index