Transport and Rate Processes in Physical, Chemical and Biological Systems "For a copy of the Solution Manual please contact Dr. Demirel: ydemirel2@unlnotes.unl.edu" To order this title, and for more information, click here Second Edition
By Yasar Demirel, University of Nebraska Lincoln, USA
Description Natural phenomena consist of simultaneously occurring transport processes and chemical reactions. These processes may interact with each
other and lead to instabilities, fluctuations, and evolutionary systems. The objective of this book is to explore the unifying role of
thermodynamics in natural phenomena. Nonequilibrium Thermodynamics, Second Edition analyzes the transport processes
of energy, mass, and momentum transfer processes, as well as chemical reactions. It considers various processes occurring simultaneously,
and provides students with more realistic analysis and modelling by accounting for possible interactions.
This second edition updates
and expands most of the chapters of the first edition by focusing on the balance equations of mass, momentum, energy, and entropy together
with the Gibbs equation for coupled processes of physical, chemical, and biological systems. Every chapter contains examples practical
problems to be solved.
This book will be effective in senior and graduate education in chemical, mechanical, systems, biomedical, tissue,
biological, and biological systems engineering, as well as physical, biophysical, biological, chemical, and biochemical sciences.
Audience
For graduate students in chemical, biological, mechanical, biomedical, environmental, and systems engineering programs, as well as for
graduate students in biophysical and biochemical science programs. Some parts may also be beneficial for advanced students in diverse
engineering programs.
Contents
Chapter 1
Fundamentals of equilibrium thermodynamics 1
1.1 Introduction 1
1.2 Basic definitions 1
1.3 Reversible and irreversible
processes 6
1.4 Equilibrium 8
Example 1.1 Equilibrium in subsystems 9
1.5 The fundamental equations 10
1.6 The thermodynamic laws
11
Example 1.2 Relationships between the molar heat capacities Cp and Cv 12
Example 1.3 Entropy and distribution of probability 14
1.7 Balance equations 14
1.8 Entropy and entropy production 16
Example 1.4 Entropy production and subsystems 17
Example 1.5 Entropy
production in a chemical reaction in a closed system 17
Example 1.6 Entropy production in mixing 18
1.9 The Gibbs equation 20
1.10
Equations of state 22
Example 1.7 Heat capacities for real gases 22
Example 1.8 van der Waals isotherms 23
Example 1.9 Estimation
of molar volume of a gas at high pressure 24
Example 1.10 Estimation of volume of a gas at high pressure using generic cubic equation
of state 25
Example 1.11 Entropy of a real gas 26
Example 1.12 Chemical potential of a real gas 27
Example 1.13 Henry?s law constant
35
Example 1.14 Estimation of partial excess properties 37
Example 1.15 Binary liquid mixture phase diagrams 39
Example 1.16 Estimation
of fugacity coefficients from virial equation 40
Example 1.17 Heterogeneous azeotrope 43
1.11 Thermodynamic potentials 46
1.12 Cross
relations 47
1.13 Extremum principles 48
Problems 49
References 52
References for further reading 52
Chapter 2
Transport and rate
processes 53
2.1 Introduction 53
2.2 Nonequilibrium systems 53
2.3 Kinetic approach 55
2.4 Transport phenomena 56
Example 2.1 Estimation
of momentum flow 59
Example 2.2 Estimation of viscosity at specified temperature and pressure 62
Example 2.3 Estimation of viscosity
of gas mixtures at low density 62
Example 2.4 Estimation of heat flow through a composite wall with constant thermal conductivities
64
Example 2.5 Estimation of heat flow with temperature-dependent thermal conductivity 66
Example 2.6 Estimation of thermal conductivity
at specified temperature and pressure 68
Example 2.7 Estimation of thermal conductivity of monatomic gases 70
Example 2.8 Estimation
of thermal conductivity of polyatomic gases 71
Example 2.9 Estimation of thermal conductivity of gas mixtures at low density 71
Example
2.10 Estimation of thermal conductivity of pure liquids 72
Example 2.11 Mass flow across a stagnant film 74
Example 2.12 Estimation
of diffusivity in a gas mixture at low density 77
Example 2.13 Estimation of diffusivity in a gas mixture at low pressure 79
Example
2.14 Estimation of diffusivity in a gas mixture of isotopes 79
Example 2.15 Estimation of diffusivity in a gas mixture 80
Example 2.16
Estimation of diffusivity of a component through a gas mixture 81
Example 2.17 Estimation of diffusivity in a dilute liquid mixture
83
2.5 The Maxwell?Stefan equations 86
2.6 Transport coefficients 87
2.7 Electric charge flow 87
2.8 The relaxation theory 89
2.9
Chemical reactions 89
2.10 Coupled processes 90
Problems 92
References 96
References for further reading 96
Chapter 3
Fundamentals
of nonequilibrium thermodynamics 97
3.1 Introduction 97
3.2 Local thermodynamic equilibrium 97
3.3 The second law of thermodynamics
98
Example 3.1 Total entropy change of an air flow in a nozzle 102
Example 3.2 Total entropy change in a polytropic compressing of
methane 103
Example 3.3 Energy dissipation in a nozzle 106
Example 3.4 Energy dissipation in a compressor 107
Example 3.5 Energy dissipation
in an adiabatic mixer 108
Example 3.6 Energy dissipation in a mixer 109
Example 3.7 Energy dissipation in a turbine 110
Example 3.8
Entropy production in a composite system 112
3.4 Balance equations and entropy production 112
Example 3.9 Conservation of energy 120
3.5 Entropy production equation 121
3.6 Phenomenological equations 127
3.7 Onsager?s relations 132
3.8 Transformation of forces and
flows 133
Example 3.10 Relationships between the conductance and resistance phenomenological coefficients 135
Example 3.11 Transformation
of phenomenological equations: dependent flows 135
Example 3.12 Transformation of phenomenological equations: dependent forces 137
Example 3.13 Transformation of phenomenological equations: dependent flows and forces 138
3.9 Chemical reactions 139
3.10 Heat conduction
139
Example 3.14 Entropy production and dissipation function in heat conduction 140
3.11 Diffusion 141
3.12 Validity of linear phenomenological
equations 142
Example 3.15 Gibbs energy and distance from global equilibrium 143
3.13 Curie?Prigogine principle 143
3.14 Time variation
of entropy production 144
Example 3.16 Entropy production and the change of the rate of entropy production with
time in heat conduction
145
3.15 Minimum entropy production 146
Example 3.17 Minimum entropy production in a two-flow system 147
Example 3.18 Minimum entropy
production in an elementary chemical reaction system 148
Example 3.19 Minimum energy dissipation in heat conduction 149
Example 3.20
Minimum entropy production in electrical circuits 151
Problems 152
References 154
References for further reading 154
Chapter 4
Using
the second law: Thermodynamic analysis 155
4.1 Introduction 155
4.2 Second-law analysis 155
Example 4.1 Lost work in throttling processes
158
Example 4.2 Dissipated energy in an adiabatic compression 159
Example 4.3 Thermomechanical coupling in a Couette flow between parallel
plates 161
Example 4.4 Thermomechanical coupling in a circular Couette flow 164
Example 4.5 Entropy production in a flow through an
annular packed bed 166
Example 4.6 Entropy production in a packed duct flow 168
Example 4.7 Heat and mass transfer 172
Example 4.8
Chemical reactions and reacting flows 174
4.3 Equipartition principle 176
Example 4.9 Entropy production in separation process: distillation
178
4.4. Exergy analysis 184
Example 4.10 Thermodynamic efficiency in a power plant 191
4.5 Applications of exergy analysis 192
Example
4.11 Energy dissipation in countercurrent and cocurrent heat exchangers 192
Example 4.12 Exergy analysis of a power plant 194
Example
4.13 Simple reheat Rankine cycle in a steam power plant 196
Example 4.14 Actual reheat Rankine cycle in steam power generation 198
Example 4.15 Ideal regenerative Rankine cycle 201
Example 4.16 Actual regenerative Rankine cycle 204
Example 4.17 Ideal reheat regenerative
cycle 208
Example 4.18 Actual reheat regenerative Rankine cycle 211
Example 4.19 Energy dissipation in a cogeneration plant 215
Example
4.20 Energy dissipation in an actual cogeneration plant 218
Example 4.21 A steam power plant using a geothermal energy source 222
Example
4.22 Exergy analysis of a refrigeration cycle 225
Example 4.23 Analysis of the Claude process in liquefying natural gas 227
Example
4.24 Power plant analysis 229
Example 4.25 Column exergy efficiency 236
Example 4.26 Assessment of separation section of a methanol
plant 237
Example 4.27 Assessment of separation of a 15-component mixture in two columns 239
Example 4.28 Assessment of separation
section of vinyl chloride monomer (VCM) plant 241
4.6 Chemical exergy 243
4.7 Depletion number 244
4.8 Optimization problem 245
4.9
Information capacity and exergy 245
4.10 Pinch analysis 246
Example 4.29 Minimum utilities by composite curve method 250
Example 4.30
Pinch analysis by temperature interval method and grand composite curve 257
Example 4.31 Column grand composite curves in a distillation
column with a five-component mixture 261
Example 4.32 Column grand composite curves in methanol plant 263
Problems 264
References
273
References for further reading 274
Chapter 5
Thermoeconomics 275
5.1 Introduction 275
5.2 Thermodynamic cost 275
Example 5.1
Cost of power generation 278
Example 5.2 Cost of power and process steam generation 278
Example 5.3 Thermoeconomic consideration of
a refrigeration system 279
5.3 Ecological cost 285
5.4 Availability 286
5.5 Thermodynamic optimum 287
Example 5.4 Minimization of
entropy production 287
5.6 Equipartition and optimization in separation systems 289
Example 5.5 Equipartition principle in separation
processes: extraction 289
Example 5.6 Thermoeconomics of extraction 291
Example 5.7 Equipartition principle: heat exchanger 292
Example
5.8 Characterization of the deviation from equipartition 294
Example 5.9 Distribution of driving forces 295
Example 5.10 Variance and
heat exchangers 295
Example 5.11 Hot fluid flow rate effect 296
Example 5.12 Equipartition principle in an electrochemical cell with
a specified duty 297
Example 5.13 Optimal distillation column: diabatic configuration 298
Example 5.14 Optimal feed state for a binary
distillation 299
Example 5.15 Retrofits of distillation columns by thermodynamic analysis 300
5.7 Thermoeconomics of latent heat storage
307
Example 5.16 Cash flow diagram for seasonal latent heat storage 312
Problems 315
References 318
References for further reading
318
Chapter 6
Diffusion 319
6.1 Introduction 319
6.2 Maxwell?Stefan equation 319
Example 6.1 Maxwell-Stefan equation for binary mixtures
322
Example 6.2 Diffusion in a ternary ideal gas mixture 330
Example 6.3 Diffusion of species from a gas mixture to a falling liquid
film 332
Example 6.4 Wetted wall column with a ternary liquid mixture 333
6.3 Diffusion in nonelectrolyte systems 335
6.4 Diffusion
in electrolyte systems 336
Example 6.5 Diffusion in aqueous solutions 338
Example 6.6 Diffusion across a membrane 339
6.5 Diffusion
without shear forces 344
Example 6.7 Binary and ternary isothermal gas mixtures 346
Example 6.8 Diffusion in a dilute isothermal gas
mixture 347
6.6 Statistical rate theory 351
Example 6.9 Transport in biological cells: osmotic and pressure driven mass transport
across
a biological cell membrane 351
Example 6.10 Prediction of diffusion coefficients of macromolecules 359
Example 6.11 Diffusion of solutes
in biological cells 359
Problems 360
References 362
References for further reading 362
Chapter 7
Heat and mass transfer 363
7.1 Introduction
363
7.2 Coupled heat and mass transfer 363
7.3 Heat of transport 369
7.4 Degree of coupling 371
7.5 Coupling in liquid mixtures 372
Example 7.1 Mass diffusion flow in term of mole fractions 372
7.6 Coupled mass and energy balances 384
7.7 Separation by thermal diffusion
387
Example 7.2 Separation by thermal diffusion 388
Example 7.3 Total energy flow and phenomenological equations 389
Example 7.4 Modified
Graetz problem with coupled heat and mass flows 390
Example 7.5 Cooling nuclear pellets 391
7.8 Nonlinear approach 394
Example 7.6
Fokker-Planck equation for Brownian motion in a temperature gradient:
short-term behavior of the Brownian particles 395
Example 7.7
Absorption of ammonia vapor by lithium nitrate-ammonia solution 399
7.9 Heat and mass transfer in discontinuous system 401
7.10 Thermoelectric
effects 406
Problems 410
References 413
References for further reading 413
Chapter 8
Chemical reactions 415
8.1 Introduction 415
8.2 Chemical reaction equilibrium constant 415
Example 8.1 Equilibrium constant of a reaction 416
Example 8.2 Equilibrium compositions
416
Example 8.3 Temperature effect on equilibrium conversion 418
8.3 The principle of detailed balance 419
8.4 Dissipation for chemical
reactions 423
8.5 Reaction velocity (flow) 425
Example 8.4 Affinity and heat of reaction 426
8.6 Multiple chemical reactions 426
Example 8.5 Conservation of mass in chemical reactions 428
Example 8.6 Calculation of entropy production for a reversible reaction 429
8.7 Stationary states 430
Example 8.7 Entropy production for series of reactions at stationary state 433
Example 8.8 Entropy production
in a homogeneous chemical system 435
Example 8.9 Chemical reactions far from global equilibrium 437
Example 8.10 Time variation of
affinity 440
Example 8.11 Time variation of entropy production in simultaneous chemical reactions 441
Example 8.12 Minimum entropy
production 442
8.8 Michaelis?Menten kinetics 443
Example 8.13 Growth of a pathogenic bacterium Brucella abortus 445
8.9 Coupled chemical
reactions 447
Problems 449
References 451
Chapter 9
Coupled systems of chemical reactions and transport processes 453
9.1 Introduction
453
9.2 Nonisothermal reaction?diffusion systems 453
Example 9.1 Effective diffusivity 455
Example 9.2 Maximum temperature difference
in the hydrogenation of benzene 459
Example 9.3 Effectiveness factor for first-order irreversible reaction-diffusion system 459
Example
9.4 Effectiveness for a first-order reversible reaction 462
Example 9.5 Maximum overall temperature difference in the hydrogenation
of benzene 464
9.3 Chemical reaction with coupled heat and mass flows 465
Example 9.6 Coupled heat and mass flows in oxidation of CH3OH
to CH2O 467
9.4 Coupled system of chemical reaction and transport processes 470
Example 9.7 Diffusion in a liquid film with a reversible
homogeneous reaction 473
Example 9.8 Stationary coupling of chemical reactions with heat and mass flows 481
Example 9.9 Chemical reaction
velocity coupled to mass flow 482
Example 9.10 Chemical reaction velocity coupled to heat flow 482
Example 9.11 Modeling of a nonisothermal
plug flow reactor 483
9.5 Evolution of coupled systems 484
9.6 Facilitated transport 485
Example 9.12 Steady-state substrate flow
in a facilitated transport 487
Example 9.13 Effect of temperature on myoglobin-facilitated transport 489
Example 9.14 Nonisothermal
facilitated transport 492
9.7 Active transport 495
Example 9.15 Long-term asymptotic solution of reversible reaction diffusion system
496
Example 9.16 Nonisothermal heterogeneous autocatalytic reactions-diffusion system 499
9.8 Nonlinear macrokinetics in a reaction?diffusion
system 500
Problems 501
References 503
References for further reading 504
Chapter 10
Membrane transport 505
10.1 Introduction 505
10.2 Membrane equilibrium 505
Example 10.1 Membrane equilibrium 507
10.3 Passive transport 508
Example 10.2 Gas permeation in a binary
gas mixture 509
Example 10.3 Time necessary to reach equilibrium in a membrane transport 514
Example 10.4 Diffusion cell with electrolytes
518
Example 10.5 Diffusion cell and transference numbers 519
Example 10.6 Estimation of flow in a diffusion cell 520
Example 10.7
Energy conversion in the electrokinetic effect 524
10.4 Facilitated and active transports in membranes 525
10.5 Biomembranes 526
Example
10.8 Coupled system of flows and a chemical reaction 534
Example 10.9 A representative active transport and energy conversions 537
Problems 538
References 539
References for further reading 540
Chapter 11
Thermodynamics and biological systems 541
11.1 Introduction
541
11.2 Simplified analysis in living systems 541
Example 11.1 Cell electric potentials 542
Example 11.2 Excess pressure in the lungs
542
Example 11.3 Enthalpy and work changes of blood due to the pumping work of the heart 543
Example 11.4 Energy expenditure in small
organisms 544
Example 11.5 Energy expenditure in an adult organism 545
Example 11.6 Oxidation of glucose 546
Example 11.7 Unimolecular
isomerization reaction 547
11.3 Bioenergetics 548
Example 11.8 Efficiency of energy conversion of photosynthesis 556
11.4 Proper pathways
557
Example 11.9 A linear pathway 562
Example 11.10 Sensitivity of the rate of the enzymatic reaction to substrate concentration 563
11.5 Coupling in mitochondria 567
11.6 Regulation in bioenergetics 574
Example 11.11 Approximate analysis of transport processes in
a biological cell 579
11.7 Exergy use in bioenergetics 581
Example 11.12 Exergy efficiency 590
Example 11.13 Approximate exergy balances
in a representative active transport 592
11.8 Molecular evolution 593
11.9 Molecular machines 593
11.10 Evolutionary criterion 595
Problems 596
References 597
References for further reading 598
Chapter 12
Stability analysis 599
12.1 Introduction 599
12.2 The
Gibbs stability theory 599
12.3 Stability and entropy production 604
Example 12.1 Distance of a chemical reaction from equilibrium
606
Example 12.2 Stability of chemical systems 607
12.4 Thermodynamic fluctuations 607
Example 12.3 Stability under both dissipative
and convective effects 608
12.5 Stability in nonequilibrium systems 608
Example 12.4 Stability of an autocatalytic reaction 610
Example
12.5 Macroscopic behavior in systems far from equilibrium 613
12.6 Linear stability analysis 614
Example 12.6 Evolution in chemical
systems 615
12.7 Oscillating systems 616
Example 12.7 Linear stability analysis: Brusselator scheme 617
Example 12.8 Linear stability
analysis with two variables 618
Example 12.9 Chemical instability 623
Example 12.10 Multiple steady states 624
Example 12.11 Reaction?diffusion
model 626
Example 12.12 Adiabatic stirred flow reactor 627
Problems 628
References 629
References for further reading 629
Chapter
13
Organized structures 631
13.1 Introduction 631
13.2 Equilibrium and nonequilibrium structures 631
13.3 Bifurcation 632
13.4 Limit
cycle 633
13.5 Order in physical structures 634
Example 13.1 Lorenz equations: The strange attractor 635
Example 13.2 Van der Pol?s
equations 637
13.6 Order in chemical systems 638
Example 13.3 The Brusselator system and oscillations 638
Example 13.4 Order in time
and space with the Brusselator system 640
Example 13.5 The Belousov?Zhabotinsky reaction scheme 643
Example 13.6 Order in time: Thermodynamic
conditions for chemical oscillations 644
13.7 Biological structures 650
Example 13.7 Chiral symmetry breaking 652
Example 13.8 Prey?predator
system: Lotka?Volterra model 654
Example 13.9 Sustained oscillations of the Lotka?Volterra type 656
Example 13.10 Lotka?Volterra model
657
Example 13.11 Enzymatic reactions: Oscillations in the glycolytic cycle 657
Example 13.12 Long-wavelength instability in bacterial
growth 660
Example 13.13 Instability in a simple metabolic pathway 661
Example 13.14 A model for an enzyme reaction inhibited by the
substrate and product 662
Problems 663
References 668
References for further reading 669
Chapter 14
Nonequilibrium thermodynamics
approaches 671
14.1 Introduction 671
14.2 Network thermodynamics with bond graph methodology 671
14.3 Mosaic nonequilibrium thermodynamics
678
14.4 Rational thermodynamics 679
14.5 Extended nonequilibrium thermodynamics 680
14.6 Generic formulations 683
14.7 Matrix model
684
14.8 Internal variables 685
References 686
References for further reading 686
Appendix 687
Appendix A 687
Tensors 687
Appendix
B 688
Table B1 Lennard-Jones (6-12) potential parameters and critical properties 688
Table B2 Collision integrals for predicting
transport properties of gases at low densities 688
Table B3 Heat capacities of gases in the ideal-gas state 689
Table B4 Heat capacities
of solids 690
Table B5 Heat capacities of liquids 691
Table B6 Properties of some common liquids 691
Table B7 Standard enthalpies
and Gibbs energies of formation at 298.15K 692
Table B8 Selected state properties 694
Table B9 Approximate standard reaction enthalpy
and standard reaction Gibbs energy
for some selected reactions at standard state T5258C, P51atm 694
Appendix C 695
Table C1 Parameters
for the thermal conductivity of alkanes in chloroform 695
Table C2 Parameters for the mutual diffusion coefficients of alkanes in chloroform
695
Table C3 Parameters for the heats of transport of alkanes in chloroform 695
Table C4 Parameters for the thermal conductivity
of alkanes in carbon tetrachloride 696
Table C5 Parameters for the mutual diffusion coefficients of alkanes in carbon tetrachloride
696
Table C6 Parameters for the heats of transport of alkanes in carbon tetrachloride 696
Appendix D 696
Table D1 Saturated water-temperature
table 696
Table D2 Superheated steam 698
Appendix E 704
Table E1 Saturated refrigerant-134a properties-Temperature 704
Table E2
Saturated refrigerant-134a properties-Pressure 705
Table E3 Superheated refrigerant-134a 706
Table E4 Ideal-gas properties of air
709
Table E5 Ideal-gas properties of carbon dioxide, CO2 711
Appendix F 713
Table F1 Values of Z0 713
Table F2 Values of Z1 714
Table F3 Values of Z0 714
Table F4 Values of Z1 715
Table F5 Values of (HR)0/RTc 716
Table F6 Values of (HR)1/RTc 717
Table
F7 Values of (HR)0/RTc 718
Table F8 Values of (HR)1/RTc 719
Table F9 Values of (SR)0/R 719
Table F10 Values of (SR)1/R 720
Table
F11 Values of (SR)0/R 721
Table F12 Values of (SR)1/R 722
Table F13 Values of f0 723
Table F14 Values of f1 724
Table F15 Values
of f0 724
Table F16 Values of f1 725
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