About Book

Thermodynamics is a branch of physics concerned with heat and temperature and their relation to energy and work. This subject has evolved since the beginning of the eighteenth century. Most studies of thermodynamics are primarily concerned with two forms of energy: heat and work. In recent years, thermodynamic research has been conducted in more systems, such as corn-ethanol biofuel cycle, lipid-peptide interactions, DNA structural motifs, and glass-forming substances. Thermodynamics is a collection of useful mathematical relations between quantities, every one of which is independently measurable. The laws of the thermodynamics provide an elegant mathematical expression of some empirically-discovered facts of nature. Thermodynamics also involves study of various types of power plants like thermal power plants, nuclear power plants, hydroelectric power plants, power plants based on renewable energy sources like solar, wind, geothermal, tides, water waves etc. The book aims to present novel ideas that are crossing traditional disciplinary boundaries and introducing a wide spectrum of viewpoints and approaches in thermodynamics. It deals with self-assembled systems, thermodynamics for ecological systems, statistical thermodynamics, surface growth, kinetics, multisite adsorption, heavy metal sorption and irreversible thermodynamics. It presents the selection of various high-level contributions involving thermodynamics. It goes from the fundamentals up to several applications in different scientific fields. The book will be of interest to those working in the fields of propulsion systems, power generation systems, chemical industry, quantum systems, refrigeration, fluid flow, combustion, and other phenomena.

Preface............................................................................................................v

Chapter 1 Minimal Dissipation Processes in Irreversible Thermodynamics and Their Applications..............................................................................1

Abstract...................................................................................................1

1. Problems and methodology of finite-time thermodynamics........2

2. Processes with a minimal dissipation...............................................5

3. Synthesis of heat exchange systems................................................11

4. The region of realizability of systems............................................17

5. Rectification processes........................................................................18

6. Conclusions..........................................................................................23

Chapter 2 The Thermodynamics of Heavy Metal Sorption onto Lignocellulosic Biomass........................................................................................................27

Abstract.................................................................................................27

1. Introduction..........................................................................................27

2. Effect of temperature on Cu(II), Ni(II), Pb(II) and Cd(II)

equilibrium...........................................................................................29

3. Conclusions..........................................................................................41

4. Conflict of Interest..............................................................................42

Chapter 3 Statistical Thermodynamics of Lattice Gas Models of

Multisite Adsorption ..............................................................................47

1. Introduction..........................................................................................47

2. The models of dimer and k-mer adsorption ...............................53

3. Multisite adsorption of orientable molecules ..............................60

4. Conclusion ...........................................................................................72

Chapter 4 Thermodynamics and Kinetics in the Synthesis of Monodisperse

Nanoparticles.............................................................................................82

1. Introduction..........................................................................................82

2. Evolution mechanism of monodisperse particles .......................83

3. Interface-controlled growth...............................................................85

4. Diffusion-controlled growth ............................................................88

5. Factors unfavorable for monodisperse distribution ......................90

6. Digestive ripening ............................................................................92

7. Digestive ripening in a binary system ..........................................96

8. Conclusions........................................................................................100

Acknowledgement ...........................................................................100

Chapter 5 Statistical Thermodynamics.................................................................103

1. Introduction........................................................................................103

2. Principles of phenomenological thermodynamics......................104

3. Principles of statistical thermodynamics......................................105

4. Ideal gas..............................................................................................108

5. Ideal crystal........................................................................................114

6. Intermolecular forces........................................................................116

7. The virial equation of state.............................................................119

8. Dense gas and liquid.......................................................................121

9. Interpretation of thermodynamic laws.........................................125

10. Acknowledgement.............................................................................127

Chapter 6 The Thermodynamics in Planck’s Law.............................................130

1. Introduction........................................................................................130

2. Mathematical results .......................................................................132

3. Derivation of planck’s law without energy quanta

[Ragazas 2010f]..................................................................................134

4. Prime physis eta and the derivation of Basic Law

[Ragazas 2010d] ...............................................................................136

5. The temperature of radiation [Ragazas 2010g]...........................139

6. The meaning and existence of Planck’s constant h

[Ragazas 2010c]..................................................................................140

7. Entropy and the second law of thermodynamics

[Ragazas 2010b].................................................................................141

8. The photoelectric effect without photons [Ragazas 2010k]......142

9. Meaning and derivation of the de broglie equations

[Ragazas 2011a].................................................................................145

10. The ‘exponential of energy’ E(t) = E0eνt

[Ragazas 2010i, 2011a]......................................................................145

11. Proposition: “If the speed of light is constant, then light is a

wave” [Ragazas 2011b]....................................................................146

12. The double-slit experiment [Ragazas 2011a]...............................146

13. Conclusion .........................................................................................149

14. Appendix: Mathematical derivations.............................................150

15. Acknowledgement.............................................................................154

Chapter 7 Thermodynamics of Surface Growth with Application to Bone Remodeling .............................................................................................157

1. Introduction........................................................................................157

2. Thermodynamics of irreversible coupled phenomena:

a survey .............................................................................................159

3. Volumetric growth............................................................................168

4. Surface growth: A review of the thermodynamics....................171

5. Model of surface growth with application to bone

remodeling ........................................................................................182

6. Concluding remarks ........................................................................192

Chapter 8 Statistical Thermodynamics of Material Transport in Non-Isothermal Mixtures ..............................................................................196

1. Introduction........................................................................................196

2. Thermodynamic theory of material transport in liquid mixtures:

Role of the Gibbs-Duhem equation...............................................196

3. Dynamic pressure gradient in open and non-stationary systems:

Thermodynamic equations of material transport with the Soret

coefficient as a thermodynamic parameter..................................201

4. Statistical mechanics of material transport: Chemical potentials

at constant volume and pressure and the Laplace component of

pressure in a molecular force field................................................203

5. The Soret coefficient in diluted binary molecular mixtures:

The kinetic term in thermodiffusion is related to the difference

in the mass and symmetry of molecules.....................................207

6. The Soret coefficient in diluted colloidal suspensions:

Size dependence of the Soret coefficient and the applicability

of thermodynamics...........................................................................210

7. The Soret coefficient in diluted suspensions of charged particles:

Contribution of electrostatic and non-electrostatic interactions to

thermodiffusion.................................................................................212

8. Material transport equation in binary molecular mixtures:

Concentration dependence of the Soret coefficient....................218

9. Conclusion..........................................................................................221

10. List of symbols..................................................................................222

Chapter 9 Some Applications of Thermodynamics for Ecological

Systems......................................................................................................228

1. Introduction........................................................................................228

2. Ecosystem as thermodynamic system...........................................229

3. Eco-exergy..........................................................................................231

4. Hypercycles........................................................................................245

5. Conclusion..........................................................................................250

6. Acknowledgments.............................................................................250

Chapter 10 The Thermodynamics of Defect Formation in Self-Assembled

Systems......................................................................................................259

1. Introduction........................................................................................259

2. Block copolymer systems................................................................268

3. Origin of defects................................................................................271

4. Graphoepitaxy....................................................................................283

5. Conclusions........................................................................................292

6. Acknowledgements...........................................................................293

Citation......................................................................................................299

Index...........................................................................................................301

About Author

Randall Davenport received his Ph.D. in Fluid Mechanics and Thermodynamics from Technological University, Enschede. He is a Visiting Professor at Public Research University, Edmonton. Davenport has contributed numerous articls and research papers on the laws of thermodynamics, internal energy, heat, work, PV diagrams, enthalpy, entropy, and free energy. His research interest areas are process systems engineering, reactor theory, thermodynamics, fluid flow, heat transfer, plant systems, chemical process modelling, and bioengineering.