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Natural phenomena consist of simultaneously occurring transport processes and chemical reactions. These processes may interact with each other and may lead to self-organized structures, fluctuations, instabilities, and evolutionary systems. *Nonequilibrium Thermodynamics, Third Edition* emphasizes the unifying role of thermodynamics in analyzing the natural phenomena.

This third edition updates and expands on the first and second editions by focusing on the general balance equations for coupled processes of physical, chemical, and biological systems. The new edition contains a new chapter on stochastic approaches to include the statistical thermodynamics, mesoscopic nonequilibrium thermodynamics, fluctuation theory, information theory, and modeling the coupled biochemical systems in thermodynamic analysis. This new addition also comes with more examples and practice problems.

Informs and updates on all the latest developments in the field Contributions from leading authorities and industry experts A useful text for seniors and graduate students from diverse engineering and science programs to analyze some nonequilibrium, coupled, evolutionary, stochastic, and dissipative processes Highlights fundamentals of equilibrium thermodynamics, transport processes and chemical reactions Expands the theory of nonequilibrium thermodynamics and its use in coupled transport processes and chemical reactions in physical, chemical, and biological systems Presents a unified analysis for transport and rate processes in various time and space scales Discusses stochastic approaches in thermodynamic analysis including fluctuation and information theories Has 198 fully solved examples and 287 practice problems AnPublisher: Elsevier ScienceReleased: Dec 16, 2013ISBN: 9780444595812Format: book

**Transport and Rate Processes in Physical, Chemical and Biological Systems **

Third Edition

Yaşar Demirel

*University of Nebraska, Lincoln, USA *

**Cover image **

**Title page **

**Copyright **

**Dedication **

**Preface to the Third Edition **

**List of Symbols **

**Greek letters **

**Subscripts **

**Superscripts **

**Chapter 1. Fundamentals of Equilibrium Thermodynamics **

**Abstract **

**1.1 Introduction **

**1.2 Basic definitions **

**1.3 Reversible and irreversible processes **

**1.4 Equilibrium **

**1.5 The thermodynamic laws **

**1.6 Balance equations **

**1.7 Entropy and entropy production **

**1.8 The Gibbs equation **

**1.9 Fluid phase equilibrium **

**Problems **

**References **

**Further Reading **

**Chapter 2. Transport and Rate Processes **

**Abstract **

**2.1 Introduction **

**2.2 Nonequilibrium systems **

**2.3 Kinetic approach **

**2.4 Transport phenomena **

**2.5 The Maxwell–Stefan equations **

**2.6 Transport coefficients **

**2.7 Electric charge flow **

**2.8 The relaxation theory **

**2.9 Chemical reactions **

**2.10 Coupled processes **

**Problems **

**References **

**Further Reading **

**Chapter 3. Fundamentals of Nonequilibrium Thermodynamics **

**Abstract **

**3.1 Introduction **

**3.2 Local thermodynamic equilibrium **

**3.3 The second law of thermodynamics **

**3.4 Balance equations and entropy production **

**3.5 Entropy production equation **

**3.6 Phenomenological equations **

**3.7 Onsager’s Relations **

**3.8 Transformation of forces and flows **

**3.9 Chemical reactions **

**3.10 Heat conduction **

**3.11 Diffusion **

**3.12 Validity of linear phenomenological equations **

**3.13 Curie–Prigogine principle **

**3.14 Time variation of entropy production **

**3.15 Minimum entropy production **

**3.16 Entropy production in an electrical circuit **

**Problems **

**References **

**Further Reading **

**Chapter 4. Using the Second Law: Thermodynamic Analysis **

**Abstract **

**4.1 Introduction **

**4.2 Second law analysis **

**4.3 Equipartition principle **

**4.4 Exergy analysis **

**4.5 Applications of exergy analysis **

**4.6 Pinch analysis **

**4.7 Optimization problem **

**Problems **

**References **

**Further Reading **

**Chapter 5. Thermoeconomics **

**Abstract **

**5.1 Introduction **

**5.2 Thermodynamic cost **

**5.3 Ecological cost **

**5.4 Availability **

**5.5 Thermodynamic optimum **

**5.6 Equipartition and optimization in separation systems **

**Problems **

**References **

**Further Reading **

**Chapter 6. Diffusion **

**Abstract **

**6.1 Introduction **

**6.2 Maxwell–Stefan equation **

**6.3 Diffusion in electrolyte systems **

**6.4 Diffusion without shear forces **

**6.5 Diffusion of biological solutes in liquids **

**Problems **

**References **

**Further Reading **

**Chapter 7. Heat and Mass Transfer **

**Abstract **

**7.1 Introduction **

**7.2 Coupled heat and mass transfer **

**7.3 Heat of transport **

**7.4 Degree of coupling **

**7.5 Efficiency of coupling **

**7.6 Coupled mass and energy balances **

**7.7 Separation by thermal diffusion **

**7.8 Heat and mass transfer in discontinuous systems **

**7.9 Thermoelectric effects **

**Problems **

**References **

**Further Reading **

**Chapter 8. Chemical Reactions **

**Abstract **

**8.1 Introduction **

**8.2 Chemical reaction equilibrium constant **

**8.3 The principle of detailed balance **

**8.4 Dissipation for chemical reactions **

**8.5 Reaction velocity (flow) **

**8.6 Multiple chemical reactions **

**8.7 Stationary states **

**8.8 Biochemical reaction networks **

**8.9 Energy conversion in coupled chemical reactions **

**Problems **

**References **

**Further Reading **

**Chapter 9. Coupled Systems of Chemical Reactions and Transport Processes **

**Abstract **

**9.1 Introduction **

**9.2 Nonisothermal reaction-diffusion systems **

**9.3 Chemical reaction with coupled heat and mass flows **

**9.4 Coupled system of chemical reaction and transport processes **

**9.5 Evolution of coupled systems **

**9.6 Nonlinear macrokinetics in a reaction-diffusion system **

**Problems **

**References **

**Further Reading **

**Chapter 10. Membrane Transport **

**Abstract **

**10.1 Introduction **

**10.2 Membrane equilibrium **

**10.3 Passive transport **

**10.4 Facilitated and active transport in membranes **

**10.5 Biomembranes **

**Problems **

**References **

**Further Reading **

**Chapter 11. Thermodynamics and Biological Systems **

**Abstract **

**11.1 Introduction **

**11.2 Simplified analysis in living systems **

**11.3 Bioenergetics **

**11.4 Proper pathways **

**11.5 Coupling in mitochondria **

**11.6 Regulation in bioenergetics **

**11.7 Reaction-mass transport in bioenergetics **

**11.8 Exergy use in bioenergetics **

**11.9 Molecular machines **

**11.10 Molecular evolution **

**11.11 Evolutionary criterion **

**Problems **

**References **

**Further Reading **

**Chapter 12. Stability Analysis **

**Abstract **

**12.1 Introduction **

**12.2 The Gibbs stability theory **

**12.3 Stability and entropy production **

**12.4 Thermodynamic fluctuations **

**12.5 Stability in nonequilibrium systems **

**12.6 Linear stability analysis **

**Problems **

**References **

**Further Reading **

**Chapter 13. Organized Structures **

**Abstract **

**13.1 Introduction **

**13.2 Equilibrium and nonequilibrium structures **

**13.3 Bifurcation **

**13.4 Limit cycle **

**13.5 Order in physical structures **

**13.6 Order in chemical systems **

**13.7 Biological structures **

**Problems **

**References **

**Further Reading **

**Chapter 14. Nonequilibrium Thermodynamics Approaches **

**Abstract **

**14.1 Introduction **

**14.2 Network thermodynamics with bond-graph methodology **

**14.3 Mosaic nonequilibrium thermodynamics **

**14.4 Rational thermodynamics **

**14.5 Extended nonequilibrium thermodynamics **

**14.6 GENERIC formulations **

**14.7 Matrix model **

**14.8 Internal variables **

**References **

**Further Reading **

**Chapter 15. Probabilistic Approach in Thermodynamics **

**Abstract **

**15.1 Introduction **

**15.2 Statistical thermodynamics **

**15.3 Stochastic thermodynamics **

**15.4 Fluctuation theorems **

**15.5 Information theory **

**15.6 Applications: biomolecules and biochemical cycles **

**15.7 Statistical rate theory **

**15.8 Mesoscopic nonequilibrium thermodynamics **

**References **

**Further Reading **

**Appendix A. Tensors **

**Appendix B. Thermochemical Parameters **

**Appendix C. Some Biochemical Reaction Properties **

**Appendix D. Steam Tables **

**Appendix E. Gas Properties **

**Appendix F. The Lee/Kesler Generalized-Correlation Tables **

**Index **

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Printed and bound in Poland

14 15 16 17 18 10 9 8 7 6 5 4 3 2 1

ISBN: 978-0-444-59557-7

**Dedication **

*To Zuhal, Selçuk and Can *

This book introduces the theory of nonequilibrium thermodynamics and its use in simultaneously occurring transport processes and chemical reactions of physical, chemical, and biological systems. Thus, it provides a unified approach in describing natural phenomena and would be used in senior and graduate education in chemical, mechanical, system, biomedical, tissue, biological, and biological systems engineering, as well as physical, biophysical, biological, chemical, and biochemical sciences.

This edition updates and revises most of the chapters of the second edition. It incorporates some of the new descriptions of the nonequilibrium thermodynamics of physical, chemical, and biological systems. In the vicinity of equilibrium, linear nonequilibrium thermodynamics provides a linear relation between forces and flows (fluxes). The laws of conventional thermodynamics involve averages of the physical properties of macroscopic systems, but ignore their fluctuations. The second law for irreversible processes states that the average entropy produced internally in an irreversible process has to be positive. Introduction of the concept of internal degrees of freedom allows for the description of a wider class of irreversible processes and scales such as biomolecules. For such a system, the probabilistic approach formulates the first law and entropy valid along fluctuation trajectories. One of the main advantages of the probabilistic approach compared to the macroscopic phenomenological theory is that a thermodynamically consistent kinetics valid beyond the linear region can be imposed. The collection of the degrees of freedom makes up the state. The change of the state, either due to the driving force or due to the fluctuations, leads to a trajectory of the system. The thermodynamic quantities like work and heat follow a distribution defined along the trajectory. The Crooks fluctuation theorem compares probability distributions for the work spent in the original process with the time-reversed one. This theorem describes how the probability of violations of the second law of thermodynamics becomes exponentially small as time or the system size increases and refines the laws of thermodynamics by taking into account the fluctuations.

Every chapter contains example problems and practice problems to be solved. **Chapter 1 was expanded in its description of basic elements of classical thermodynamics, such as irreversibility, equilibrium state, thermodynamic principles, the Gibbs equation, and the phase equilibria. Chapter 2 briefly introduces transport processes, chemical reactions, thermodynamic branch, and some well-known examples of coupled phenomena. Chapter 3 discusses the general balance equations, which are used in the Gibbs equation to derive the rate of entropy production based on local equilibrium. Chapter 4 focuses on thermodynamic analysis of transport processes, power-generating systems, and chemical reactions. It also introduces the concept of exergy, the equipartition principle, and pinch analysis with various example problems to underline the contribution of thermodynamic analysis towards creating optimum designs and assessing the performance of existing designs. Chapter 5 introduces the thermodynamic optimum approach in the design and optimization of various processes. Here, the concept of thermoeconomics is emphasized. Chapter 6 summarizes the diffusion in nonelectrolyte and electrolyte systems and explores some related applications. Chapter 7 describes coupled heat and mass transfer and the level of coupling without chemical reaction. Chapter 8 briefly summarizes chemical reactions and coupled phenomena. Chapter 9 describes coupled transport processes and chemical reactions; it focuses on the dynamic balance equations consisting of coupled flows as well as the coupling between chemical reactions and the flows of heat and mass. Chapter 10 briefly describes the nonequilibrium formulations of the transport through membranes. Chapter 11 introduces various applications of thermodynamics in biological systems as well as energy conversion and coupling phenomena in bioenergetics. It also discusses the facilated and active transport in biological systems. Based on the nonequilibrium thermodynamic approach, the stability aspects of various transport processes and chemical reactions are covered in Chapter 12. Chapter 13 briefly describes some organized structures maintained with the outside supply of energy and matter. Some biological systems are good examples of maintaining dissipative organized structures. Chapter 14 summarizes some of the other thermodynamic approaches, such as extended nonequilibrium thermodynamics. Chapter 15, as a new addition, introduces statistical thermodynamics for stochastic thermodynamics approach, fluctuation theorems, information theory, and biological applications. The probabilistic approach reached the broader appeal due to advances in experimental techniques for tracking and manipulating of single particles and molecules. Future research in the field may focus on specific applications, most likely for molecular motors, biomolecular networks, and information processing. The appendix supplies some data needed in the example and practice problems. **

All through the editions, the work of many people who contributed to both the theory and applications of thermodynamics for transport and rate processes in physical, chemical, and biological systems has been visited and revisited. I acknowledge and greatly appreciate the contributions of all these people. I am also thankful to colleagues, students, and reviewers who have contributed with their comments and suggestions over the past 15 years of evolution of the current edition.

**Yaşar Demirel **

**2013 **

** a activity, **interfacial area

** A Helmholtz **free energy, chemical affinity

** A∗ nondimensional **affinity

** B, C virial **coefficients

**Be **Bejan number

**Br **Brinkman number

** c concentration, **cost

** Cp, Cv heat **capacities at constant-pressure and constant-volume, respectively

**D **diffusion coefficient, diameter

**Da **Damköhler number

*e *energy

** ex specific **exergy

** E activation **energy of the chemical reaction, energy

*Ex *exergy

** f fugacity **of pure component

** fi fugacity **of species in a mixture

**F **force

** g acceleration **of gravity

** G Gibbs **free energy

**Δ Gr **Gibbs free energy change on reaction

**Δ Hr **reaction enthalpy

** h enthalpy **(specific)

** H enthalpy, **Henry’s law constant

** I electric **current

** J diffusive **mass flux

** Jq conduction **heat flux

** Jr **reaction velocity

** k thermal **conductivity

** kB **Boltzmann constant

** K chemical **equilibrium constant

** Kij resistance **coefficients

** ke **effective thermal conductivity

** kv first-order **reaction rate constant

** L characteristic **half thickness

**Le **Lewis number

** Lik phenomenological **coefficients (conductance)

*m *mass

** M molecular **weight

** n number **of components

** N number **of moles

**Nu **Nusselt number

** P pressure, **volumetric rate of entropy production

**Pe **Peclet number

**Pr **Prandtl number

** Pi partial **pressure of species

** Pr **reduced pressure

** qij degree **of coupling between processes i and j

**q **heat flow vector

** Q volumetric **flow

** R gas **constant

**Re **Reynolds number

** s specific **entropy

*S *entropy

**Sc **Schmidt number

** Sprod **entropy production

*t *time

*T *temperature

** Tr **reduced temperature

** u specific **internal energy

** U internal **energy

**v **velocity vector

*V *volume

** w mass **fraction

*W *work

** Ws **shaft work

** x liquid **mole fraction, ratio of forces

** X thermodynamic **force

** y vapor-phase **mole fraction

** z dimensionless **distance

** Z compressibility **factor

** α eigenvalues, **thermal diffusivity

** α coefficient **of thermal expansion

** β thermal **expansion, thermicity group

** γ specific **heat ratio, Arrhenius group, dimensionless

** γi activity **coefficient

** δij Kronecker **delta function

**ε **dimensionless coefficient related to Soret effect, extent of a chemical reaction, elasticity coefficient

** η efficiency, **shear viscosity

** θ dimensionless **concentration

** κ isothermal **compressibility

** κs isentropic **compressibility

** λ controlling **parameters

** μ chemical **potential, viscosity

**ν **stoichiometric coefficients, kinematic viscosity

**Π **osmotic pressure

*ρ *density

**σ **local entropy generation rate

** τ dimensionless **time

** ϕ Thiele **modulus

** φ dimensionless **temperature

**Ψ **dissipation function, dissipated available energy

** ω accentric **factor, dimensionless parameter related to Dufour effect

**av **average

**az **azeotrope

**b **backward, bulk

**c **critical, charging

**d **discharging

**D **Dufour

**e **effective

**eq **equilibrium state

**EOS **equation of state

**f **forward, formation

**liq **liquid

**L **liquid

**m **melting

**min **minimum

**mix **mixing or mixture

**opt **optimum

**p **packed

**prod **production

**q **heat

**r **reaction, reduced property

**rev **reversible

**s **surface, isentropic

**sat **property along a two-phase coexistence line

**S **Soret

**th **thermodynamic

**V **vapor

**vap **vapor

**E **excess

**R **reduced

**sat **saturation

**. **rate

**0 **reference (initial) conditions

**o **standard conditions

**Chapter 1 **

**Fundamentals of Equilibrium Thermodynamics **

Thermodynamics is a science of energy in which temperature—as it is related to the average of molecular motions—is an important concept. Guggenheim defines thermodynamics as that part of physics concerned with any equilibrium property’s dependence on temperature. Thermodynamics also formulates the average changes taking place among large numbers of molecules; therefore, it is a macroscopic science. Carnot, Rankine, Clausius, Kelvin, Gibbs, and many others developed formulations of thermodynamic principles for describing the conservation and conversion of energy. The theoretical formulation of classical thermodynamics is a set of natural laws governing the behavior of macroscopic systems; these laws lead to a large number of equations and axioms that are exact, based entirely on logic, and attached to well-defined constraints. As natural phenomena are far from reversible, adiabatic, isothermal, equilibrium, or ideal, the engineer must exercise a pragmatic approach in applying the principles of thermodynamics to real systems. Some new texts have attempted to present thermodynamic principles and formulations in ways applicable to students and engineers, which would allow the formulations to be applied in modeling, designing, and describing some natural and complex phenomena. Principles of thermodynamics find applications in all branches of engineering and the sciences. Besides that, thermodynamics may present methods and generalized correlations

for the estimation of physical and chemical properties when there are no experimental data available. Such estimations are often necessary in the simulation and design of various processes. This chapter briefly covers some of the basic definitions, principles of thermodynamics, entropy production, the Gibbs equation, phase equilibria, equations of state, and thermodynamic potentials.

The name thermodynamics stems from the Greek words *therme *(heat) and *dynamis *(power). Thermodynamics is a science of energy in which temperature—as it is related to the average of molecular motion—is an important concept. Guggenheim defines thermodynamics as that part of physics concerned with any equilibrium property’s dependence on temperature. Thermodynamics also formulates the average changes taking place among large numbers of molecules; therefore, it is a macroscopic science.

Thermodynamics first emerged as a science after the construction and operation of steam engines in 1697 by Thomas Savery and in 1712 by Thomas Newcomen in England. Later, Carnot, Rankine, Clausius, Kelvin, Gibbs, and many others developed formulations of thermodynamic principles for describing the conservation and conversion of energy. The theoretical formulation of classical thermodynamics is a set of natural laws governing the behavior of macroscopic systems; these laws lead to a large number of equations and axioms that are exact, based entirely on logic, and attached to well-defined constraints. As natural phenomena are far from reversible, adiabatic, isothermal, equilibrium, or ideal, the engineer must exercise a pragmatic approach in applying the principles of thermodynamics to real systems. Some new texts have attempted to present thermodynamic principles and formulations to be applied in modeling, designing, and describing some natural and complex phenomena.

Principles of thermodynamics find applications in all branches of engineering and the sciences. Besides that, thermodynamics may present methods and generalized correlations

for the estimation of physical and chemical properties when there are no experimental data available. Such estimations are often necessary in the simulation and design of various processes. This chapter briefly covers some of the basic definitions, principles of thermodynamics, entropy production, the Gibbs equation, phase equilibria, equations of state, and thermodynamic potentials.

A thermodynamic system is a part of the physical universe with a specified boundary for observation. A *system *contains a substance with a large amount of molecules or atoms, and is formed by a geometrical volume of macroscopic dimensions subjected to controlled experimental conditions. An ideal thermodynamic system is a model system with simplifications to represent a real system that can be described by the theoretical thermodynamics approach. A *simple system *is a single state system with no internal boundaries, and is not subject to external force fields or inertial forces. A *composite system*, however, has at least two simple systems separated by a barrier restrictive to one form of energy or matter. The *boundary *of the volume separates the system from its *surroundings*. A system may be taken through a *complete cycle *of states, in which its final state is the same as its original state.

In a *closed system*, a material content is fixed and an internal mass changes only due to a chemical reaction. Closed systems exchange energy only in the form of heat or work with their surroundings. In an *open system, *material and energy contents are variable, and the systems freely exchange mass and energy with their surroundings. *Isolated systems *cannot exchange energy and matter. A system surrounded by an insulating boundary is called a thermally *insulated system*. A system and its surroundings are considered the *universe*.

The properties of a system based on the behavior of molecules are related to the *microscopic state*, which is the main concern of *statistical thermodynamics*. On the other hand, *classical thermodynamics *formulates the *macroscopic state*, which is related to the average behavior of large groups of molecules leading to the definitions of macroscopic properties such as temperature and pressure. The macroscopic state of a system can be fully specified by a small number of parameters, such as the temperature, volume, and number of moles. The classical mechanical description of the microscopic state of fluid systems the position vector and velocity vector of each particle would be specified.

Energy through its conversion and degradation can cause physical and chemical processes to occur. A process takes place in a system. Any process within an adiabatic system is known as an *adiabatic process*. A process that takes place with only an infinitesimal change in the macroscopic properties of a system is called an *infinitesimal process*. The classification of processes according to Planck considers three independent infinitesimal processes. They are *natural processes*, *unnatural processes*, and *reversible processes*. Natural processes actually occur and always proceed in a direction toward equilibrium. Unnatural processes are those that proceed in a direction away from equilibrium and never occur. A reversible process is a case between natural and unnatural processes and proceeds in either direction through a continuous series of equilibrium states. Guggenheim provides the following simple example: consider the evaporation of a liquid at an equilibrium pressure *P*eq. If *P* *<* *P*eq, a natural evaporation takes place. However, when *P* *>* *P*eq, the evaporation is unnatural. If *P* = *P*eq *−* *δ, *where *δ* > 0, evaporation takes place, and in the limit *δ* → 0 the process becomes reversible.

In a *steady state process *the variables in a system remain constant with time, while in an *unsteady state process *or in a *transient process *the variables change with time. At steady state, a system exchanges energy or matter at a constant rate.

Thermodynamic macroscopic properties or coordinates are derived from the statistical long time averaging of the observable microscopic coordinates of motion. For example, the pressure we measure is an average over about 10²⁴ molecule-wall collisions per second per square centimeter of surface for a gas at standard conditions. If a thermodynamic property is a *state function*, its change is independent of the *path *between the initial and final states, and depends only on the properties of the initial and final states of the system. The infinitesimal change of a state function is an exact differential.

Properties like mass *m *and volume *V *are defined by the system as a whole. Such properties are additive, and are called *extensive properties*. Separation of the total change for a species into the external and internal parts may be generalized to any extensive property. All extensive properties are homogeneous functions of the first order in the mass of the system. For example, doubling the mass of a system at constant composition doubles the internal energy.

The pressure *P *and temperature *T *define the values at each point of the system and are therefore called *intensive properties*, some of which can be expressed as derivatives of extensive properties, such as temperature

where *U *is the energy and *S *is the entropy. If *X *denotes any extensive property (not necessarily a thermodynamic property) of a phase, we may derive intensive properties denoted by *Xi *(*i *≠ *j*at constant *T *and *P*.

Energy is a conserved and extensive property of every system in any state, and hence its value depends only on the state. Work, on the other hand, is not a property of a system. Energy may be transferred in the forms of heat or work through the boundary of a system. In a complete cycle of steady state process, internal energy change is zero and hence the work done on the system is converted to heat (|work|=|heat|) by the system. The mechanical work of expansion or compression proceeds with the observable motion of the coordinates of the particles of matter. Chemical work, on the other hand, proceeds with changes in internal energy due to changes in the chemical composition (mass action). *Potential energy *is the capacity for mechanical work related to the position of a body, while *kinetic energy *is the capacity for mechanical work related to the motion of a body. Potential and kinetic energies are external, while sensible heat and latent heat are internal energies.

During a process, energy can be transferred and converted from one form to another, while the total energy remains constant. This is known as the *conservation of energy *principle.

Entropy *S *is a nonconserved and extensive property of a system in any state and its value is part of the state of the system. Any change of state is associated with a change in entropy. Entropy change is determined by the following equation:

where *δq*rev is the reversible heat flow. When a fluid system changes from state *A *to state *B *by an irreversible process, then the change of its entropy is be Δ*S* *=* *S*B *−* *S*A. Some important properties of entropy are:

; the inequality is for a natural change; the equality is for a reversible change.

, where *d*e*S *is the change due to the interaction of a system with its surroundings, and *d*i*S *is the increase due to an internal natural change, such as a chemical reaction, is always positive for irreversible changes (*d*i*S* > 0) and zero at equilibrium (*d*i*S* = 0).

• The entropy of a system is the sum of the entropies of all changes within the system.

• The entropy of an insulated closed system remains constant in any reversible change, increases in any natural change, and reaches a maximum at equilibrium.

• For any complete cycle, the change of entropy is zero.

For constant mass, some general property relations in terms of temperature and pressure are

by *dP *at constant temperature and using the Maxwell relations, we have

Therefore, Eqn **(1.1) becomes **

where *β *. Similarly, the changes in entropy and volume become

where *κ *is from the Maxwell relations. **Table 1.1 shows the coefficients of thermal expansion and isothermal compressibility of gas state for some compounds at 298.15 K at 1 atm. **

**Table 1.1 **

**Coefficients of Thermal Expansion and Isothermal Compressibility of Some Gas Compounds at T = 298.15 K and P = 1 atm **

*Source*: **Kondepudi and Prigogine (1999). **

Integration of Eqn **(1.1) computes the finite change in enthalpy in an actual process from equilibrium state ( T1,P1) to equilibrium state (T2,P2). This integration must be done over a reversible path **

As the enthalpy is a state function, the change in enthalpy Δ*H *is independent of the path selected for integration. The change between two states can be calculated by a chosen path, such as first an isothermal expansion from *P*1 to *P*2 at *T*1 followed by isobaric heating from *T*1 to *T*2 at *P*2 and isothermal compression from *P*2 to *P*3 at *T*2

Using an alternative path of isobaric heating from *T*1 to *T*2 at *P*1 followed by isothermal compression from *P*1 to *P*3 at *T*2, then we have

With small changes in *T *and *P*, and constant values of *β *and *κ*, integration of Eqn **(1.3) yields **

For ideal gases, we have

The gas constant *R *is common to all gases and determined by the product of the Boltzmann constant and the Avogadro number: *R* = (1.3805 × 10−23) J/K (6.0225 × 10−23) 1/mol = 8.3143 J/(mol K). For liquids, we have

**(1.4) **

**(1.5) **

For incompressible fluids, thermal expansion *β *and isothermal compressibility *κ *are practically zero, and Eqns **(1.4) and (1.5) become **

Entropy change for solid and liquids is

**Table 1.2 shows the heat capacities at constant pressure and volume for some gas compounds at 298.15 K and 1 atm. Tables B3 to B5 in Appendix B list the heat capacities of various compounds as function of temperatures in the form of **

where *a*, *b*, *c*, and *d *are the parameters.

**Table 1.2 **

**Molar Heat Capacities for Some Gas Compounds at T = 298.15 K and P = 1 atm **

*Source*: **Kondepudi and Prigogine (1999). **

For constant mass, some general property relations in terms of temperature and volume are

and

**(1.7) **

From the following Maxwell relations, thermal expansion *β*, and isothermal compressibility *κ*, we have

by *dV *at constant temperature and using the Maxwell relations, we have

and

Therefore, Eqns **(1.6) and (1.7) become **

The second partial derivatives of the state functions at constant volume and entropy are

where *Cv *is the heat capacity at constant volume, *β*S the adiabatic thermal expansion, and *κ*S the compressibility. The second partial derivatives of the state functions at constant pressure and temperature are

The following transforming derivatives are widely used in thermodynamic derivations.

• Triple product rule for *F = F*(*x,y*)

• Chain rule

• Commutative property

**(1.12) **

• Jacobian matrix *J *for functions of two variables *f*(*x,y*) and *g*(*x,y*)

**(1.13) **

.

Use the triple product rule for

.

Determine the dependence of *Cp *on pressure at constant temperature.

To determine the dependence of *Cp *on pressure at constant temperature, we start with Eqn **(1.1) **

We note that

leads to

The dependence of *Cp *on pressure at constant temperature becomes

Using data for *Cp *as a function of *T *at a pressure *P*1 to estimate *Cp *as a function of *T *at different pressure *P*2, we integrate the equation above at temperature *T *as follows:

Here the partial differential term can be calculated from an equation of state. Heat capacity data are available at very low pressures or at very large specific volume, where all fluids are ideal gases:

As seen in **Appendix B, Table B3, data of Cp for states at low pressure are expressed by **

To determine the effect of pressure on the heat capacity, we have

Similarly, for the effect of volume, we have

If the partial derivative inside the integral is determined from an equation of state, then the heat capacity of a real gas can be calculated.

Derive expressions for the difference *Cp* − *Cv *for (a) ideal gas and (b) real gas.

Start with Eqn **(from Example 1.1) to find **

From Eqn **(1.5) and the equation above, we have **

**(a) **

Equation **(a) yields a general relation between Cp and Cv **

For ideal gases (*PV* = *RT*):

For real gases:

. Tables B3 to B5 in **Appendix B list the temperature-dependent heat capacity data for ideal gas, liquids, and solids at 298.15 K. **

For pure ideal systems, the chemical potential is expressed by

**(1.14) **

where *To *and *Po *are the reference temperature and pressure, and *xj *is the mole fraction of species *j*. Chemical potential can only be defined relative to its value at the arbitrary reference state. The chemical potential can also be defined in terms of the concentration of species *j*, *cj* = *Nj/V *

For nonideal systems, we use an activity in place of concentration, and Eqn **(1.14) becomes **

**(1.15) **

where *F *is the Faraday, or electric charge per mole (*F* = 96,500 coulombs/mol), *zj *is the valence of the species *j*, and *ψ *is the electric potential.

The absolute activity is related to the molar chemical potential by

**(1.16) **

The absolute activity is often used in phase equilibrium. For example, the equilibrium condition for the distribution of species *i *between vapor and liquid phases is

Consider the equations that describe time-dependent physical processes; if these equations are invariant with regard to the algebraic sign of the time, the process is called a *reversible process*; otherwise it is called an *irreversible process*. Reversible processes are macroscopic processes that occur in the vicinity of global equilibrium. We can reverse the reversible process at any stage by a slight change in an external parameter. Guggenheim describes the reversible process and reversible change as follows: a process in a system interacting with its surroundings is a *reversible process *if the system and its surroundings are in equilibrium throughout the process. If equilibrium is not established, the result is a *reversible change*. For example, if heat flows from one system in equilibrium to another system in equilibrium, then a reversible change occurs; it is not a reversible process unless these two systems are at the same temperature. In a reversible process, it would be possible to perform a second process in at least one way to restore the system and its environment to their respective original states, except in the case of differential changes higher than the first order. A reversible process proceeds with infinitesimal driving forces (i.e. gradients) within the system. Hence, for a linear transport system, reversible change occurs slowly on the scale of macroscopic relaxation times, and dissipative effects cannot be present. Time appears only through its arithmetic value in the equations for reversible processes. For example, the equation describing the propagation of waves in a nonabsorbing medium is

where *c*o is the velocity of propagation and *u *is the amplitude of the wave. The equation above is invariant in the substitution of *t *for (−*t*); hence the propagation of waves is a reversible process.

For a simple reversible chemical reaction, if one path is preferred for the backward reaction, the same path must also be preferred for the reverse reaction. This is called the principle of *microscopic reversibility*. Time can be measured by reversible, periodic phenomena, such as the oscillations of a pendulum. However, the direction of time cannot be determined by such phenomena; it is related to the unidirectional increase of entropy in all natural processes. Some ideal processes may be reversible and proceed in forward and backward directions.

The Fourier equation

is not invariant with respect to time, and it describes an irreversible process. The term *α *is the thermal diffusivity. Irreversibility is a consequence of the dynamics of collisions in which the transfer of mass, energy, and momentum takes place. Hydrodynamics specifies a number of nonequilibrium states by the mass density, velocity, and energy density of the fluid. Hydrodynamic equations thus comprise a wide range of relaxation processes, such as heat flow, diffusion, or viscous dissipation, which are all irreversible.

Entropy in an isolated system increases *dS/dt* > 0 until it reaches equilibrium *dS/dt* = 0, and displays a direction of change leading to the thermodynamic arrow of time. The phenomenological approach favoring the retarded potential over the solution to the Maxwell field equation is called the time arrow of radiation. These two arrows of time lead to the Einstein–Ritz controversy: Einstein believed that irreversibility is based on probability considerations, while Ritz believed that an initial condition and thus causality is the basis of irreversibility. Causality and probability may be two aspects of the same principle since the arrow of time has a global nature.

The term irreversibility has two different uses and has been applied to different arrows of time

. Although these arrows are not related, they seem to be connected to the intuitive notion of causality. Mostly, the word irreversibility refers to the direction of the time evolution of a system. Irreversibility is also used to describe noninvariance of the changes with respect to the nonlinear time reversal transformation. For changes that generate space–time symmetry transformations, irreversibility implies the impossibility to create a state that evolves backward in time. Therefore, irreversibility is time asymmetry due to a preferred direction of time evolution.

Time is manifest in the movement of a system toward equilibrium, at which it has no events that may be used to measure time. Both the equilibrium steady-state

of generation and consumption of chemical species, and the stable, dynamic, steady state that exists far from equilibrium, are characterized by time-independent molecular distributions. It seems that the degree of organization within either system, equilibrium, or dissipative, is timeless. Essentially, time is dependent on a system’s distance from equilibrium. A dissipative structure existing in a stable steady state may be seen as a storing time.

Some examples of reversible processes are uniform and slow expansion or compression of a fluid, such as fluid flows in a well-designed turbine, compressor, nozzle, or diffuser.

• Reversible processes are differentially removed from equilibrium with no (appreciable) internal temperature, pressure, and velocity changes.

• A reversible process can be reversed at any point by external conditions.

• Time-dependent reversible processes are invariant with regard to the algebraic sign of the time.

• Reversible processes traverse a succession of equilibrium states.

• A reversible process represents a limit to the performance of actual processes.

.

• For a given change of state the surroundings extract maximum possible work from the system if the process is carried out reversibly.

• If the surroundings are doing work on the system, for a given change of state, a minimum amount of work is needed if the process occurs reversibly.

Some examples of irreversible processes are electric current flow through a conductor with a resistance, magnetization or polarization with hysteresis, inelastic deformation, fluid flow with shock wave, and mixing of fluid with different temperatures, pressures, and/or compositions.

• Irreversible processes are actual processes carried out in finite time with real substances with internal temperature, pressure, and/or velocity changes causing energy dissipation, such as viscous dissipation.

• Equations that describe time-dependent processes are not invariant with the algebraic sign of time.

• No infinitesimal change in external conditions can reverse process direction.

• In irreversible processes, heat transfer occurs through a finite temperature difference.

• In irreversible processes, mass transfer occurs through a finite chemical potential difference.

• An example of an irreversible process is a spontaneous chemical reaction, or an electrochemical reaction.

• Irreversible processes are characterized by the flow of fluids with friction.

• Δ*S*total > 0 means that no single process is possible for which the total entropy decreases.

.

If a physical system is isolated, its state changes irreversibly to a time-invariant state in which no physical or chemical change occurs, and a state of equilibrium is reached in a finite time. A change in a stable equilibrium state causes net effects either in the environment of the system or the values of amounts of constituents and parameters within the system itself. Some conditions of equilibrium for a system thermally insulated with an infinitesimal change are

• At constant volume: *dS* = 0, *dV* = 0, *dU* = 0;

• At constant pressure: *dS* = 0, *dP* = 0, *dH* = 0;

• At constant volume and temperature: *dA* = 0, *dV* = 0, *dT* = 0; and

• At constant pressure and temperature: *dG* = 0, *dT* = 0, *dP* = 0.

• The entropy of an isolated system reaches the maximum possible value at equilibrium.

• For a closed system

For entropy to remain constant, we keep *T*, *V*, and *dNi *constant, and the entropy produced, *d*i*S*, has to be removed from the system. The decrease in energy is generally due to the conversion of mechanical energy into heat.

• The Helmholtz free energy reaches a minimum possible value at equilibrium.

• The Gibbs free energy reaches a minimum possible value at equilibrium.

• The enthalpy reaches a minimum possible value at equilibrium.

The conditions of equilibrium can be established in terms of extensive parameters *U *and *S*, or in terms of intensive parameters. Consider a composite system with two simple subsystems of *A *and *B *having a single species. Then the condition of equilibrium is

Hence the thermal, mechanical, and chemical equilibrium conditions in terms of the intensive properties are

since *dS*A, *dV*A, and *dμ*A are the infinitesimal changes in independent variables. Similarly, the equilibrium conditions are expressed in terms of entropy

and the equilibrium conditions become

At equilibrium, all the irreversible processes vanish, and temperature, pressure, and chemical potentials become uniform; this means that no thermodynamic force exists in the system. No perturbation will cause a change in a neutral equilibrium. Any two phases in *hydrostatic equilibrium *must have the same pressure; in *thermal equilibrium*, any two phases must have the same temperature. If two phases are in equilibrium with respect to any species, then the chemical potential of that species must have the same value in these phases.

Consider an elementary general chemical reaction:

where *ν*S and *ν*P are the stoichiometric coefficients. The condition for chemical equilibrium is

**(1.18) **

where *μi *is the chemical potential of a species *i*. This *chemical equilibrium *condition is equivalent to the vanishing affinity *A *defined by

**(1.19) **

The emergence of macroscopic reversibility from microscopic irreversibilities is referred to as *dynamic equilibrium *with the mechanisms of cancellation of the opposite molecular processes.

A system may be in a *stable, metastable, unstable, *or *neutral equilibrium *state. In a stable system, a perturbation causes small departures from the original conditions, which are restorable. In an unstable equilibrium, even a small perturbation causes large irreversible changes. A metastable system may be stable or unstable according to the level and direction of perturbation. All thermodynamic equilibria are stable or metastable, but not unstable. This means that all natural processes evolve toward an equilibrium state, which is a global attractor.

, are the fundamental principles of stable equilibrium, and can be associated with thermodynamic stability, although the stability of equilibrium is not unique to thermodynamics.

Consider a closed isolated cylinder with two subsystems of 1 and 2 containing air with an equal volume of 1 l and equal temperatures of 298.15 K. There is a fixed piston at the boundary of the subsystems, which have different pressures of *P*1 = 2 atm and *P*2 = 1 atm. Estimate the temperature, volume, and pressure of the subsystems when the piston is released. Assume that the piston is impermeable to air, freely movable, and heat conducting.

Assume that the air is an ideal gas with constant heat capacity.

The initial states (*i*) of the subsystems are

**(a) **

In the final state (*f*), we have

.

According to the first law and constant heat capacity *Cv*, we have

This is a natural result as the internal energy of an ideal gas depends on the temperature only, and the system is isothermal at the initial and final conditions.

From Eqns **(a) and (b), we have **

With a total volume of 2 l, the final volumes and pressures become

A set of thermodynamic laws governing the behavior of macroscopic systems lead to a large amount of equations and axioms that are exact, based entirely on logic, and attached to well-defined constraints. These laws are summarized in the following sections.

Two systems in thermal contact eventually arrive at a state of thermal equilibrium. Temperature, as a universal function of the state and the internal energy, uniquely defines the thermal equilibrium. If system 1 is in equilibrium with system 2, and if system 2 is in equilibrium with system 3, then system 1 is in equilibrium with system 3. This is called the *zeroth law of thermodynamics *and implies the construction of a universal temperature scale (stated first by Joseph Black in the eighteenth century, and named much later by Guggenheim). If a system is in thermal equilibrium, it is assumed that the energy is distributed uniquely over the volume. Once the energy of the system increases, the temperature of the system also increases (*dU*/*dT* > 0).

A change in a state function accompanying the transition of a system from one state to another depends only on the initial and final states and not on the path between these states. If the system returns to its original state, the integral of the change is zero

Such systems are called *cyclic processes*. The Poincare statement of the first law states that in a cyclic process, the work done by the system equals the heat received by it.

According to the first law of thermodynamics, the state function of internal energy *U *in a closed system is equal to the sum of the heat received by the system *δq *and the mechanical work *δW *performed on the system by the surroundings

**(1.20) **

The definition and existence of energy as a property of every system in any state is an important consequence of the first law. Changes of heat and work depend on the path of a change and are not state functions. The symbol *δ *is used throughout the text to indicate differentials of path-dependent functions that are not state variables.

Assume that collinear unidirectional vector is represented by its magnitude only. For a rigid body subject to both boundary and body forces, Newton’s second law of motion is

**(1.21) **

where *Fs *is the force vector acting on the surface of the rigid body and *Fb *is the body force associated with external fields, such as gravitational, inertial, coulombic, etc. If *Fs *causes the weight of a body rises during the motion, Eqn **(1.21) yields **

Where *dv*/*dt *is the acceleration vector *a *(*F* = *ma*). The mechanical work *W *associated with the movement of a rigid body is the scalar product of the net force and displacement vectors *dz *

The total work on the weight between states 1 and 2 is

The first and second terms on the right are the difference in potential and kinetic energy, respectively.

The *sign convention *adapted here assumes that heat transferred into the system from the surroundings is positive, and work transferred into the system (work done on the system) at which energy is transferred into the system from the surroundings is positive. For compression work we have *δW* = −*PdV *as the compression leads to −*dV *and positive work. The signs of heat and work referring to the surroundings would then be opposite *q*sur = −*q *and *W*sur = −*W*.

In general, the term *δW *represents all different forms of work. Work is the product of an intensive variable and a differential of an extensive variable. For example, if the system is displaced by a distance *dl *under a force *F*, it performs the work of −*Fdl*. If −*dNi* moles of substance *i *with the chemical potential *μi *flow from the system to its surroundings, the chemical work of −*μdNi *occurs. Thus the total work becomes

Here −*PdV *refers to the sign convention recommending that work done on the system is positive as the compression work leads to −*dV *and positive work. Some other types of work interactions are surface deformation (*σdA*, where *σ *is the surface tension and *dA *is the change in surface area), electric polarization, magnetic polarization, frictional, and stress–strain.

For an open system, an additional contribution to the energy due to the exchange of matter (*dUm*) occurs

For systems with chemical reactions, the total energy may be considered as a function of *T*, *V*, and *Ni*: *U* = *U*(*T,V,Ni*). The total differential of *U *is

The exact form of the function *U*(*T,V,Ni*) for a certain system is obtained empirically.

The work of Carnot, published in 1824, and later the work of Clausius (1850) and Kelvin (1851), advanced the formulation of the properties of entropy, temperature, and the second law. Clausius introduced the word entropy. The second law is a statement of existence of stable equilibrium states and distinguishes thermodynamics from mechanics and other fields of physics. The many stable equilibrium states and various other equilibrium and nonequilibrium states contemplated in thermodynamics are not contemplated in mechanics (**Gyftopoulos and Beretta, 2005). The second law is a qualitative statement on the accessibility of energy and the direction of progress of real processes. For example, the efficiency of a reversible engine is a function of temperature only, and efficiency cannot exceed unity. These statements are the results of the first and second laws, and can be used to define an absolute scale of temperature that is independent of any material properties used to measure it. A quantitative description of the second law emerges by determining entropy and entropy production in irreversible processes. **

If a system is in equilibrium, then all the forces *Xi *are fully known from external parameters *ai*, so that the first law is

**(1.23) **

The equation above is a Pfaffian equation and *ai *and ideal gas Eqn **(1.23) becomes **

**(1.24) **

, *q *is path dependent and *dq *is replaced by *δq*. However, it is possible to find a function *T* = *T*(θ), where θ is some chosen temperature, to be used in Eqn **(1.24) as an integrating factor 1/ T, then we have the following exact Pfaffian differential form (Pogliani and Berberan-Santos, 2000), which satisfies the exact differential criterion **

Then (*δq/T*) becomes a state function called entropy and *T *the absolute temperature. As a state function, entropy is path-independent. Eqn **(1.25) is a mathematical statement of the second law of thermodynamics. The introduction of the integrating factor for δq causes the thermal energy to be split into an extensive factor S and an intensive factor T. Clausius defined the entropy with the integrating factor of the inverse of absolute temperature in 1/T(δq) = dS. Similarly, integrating factor 1/P in 1/P(δW) = dV leads to exact differential dV, which is formulated by Clapeyron in 1834. Introducing Eqn (1.25) into the first law of thermodynamics dU = δq + δW yields the combined first and second laws of thermodynamics **

**(1.26) **

The equation above represents a special case of the first law applied to an infinitesimal quasi-static path of a closed system.

Every system is associated with an energy and entropy. When a system changes from one state to another, the total energy remains constant. However, the total entropy is not conserved, and increases in irreversible processes while remaining unchanged in reversible processes. The notion of entropy is not a directly intuitive concept. We can relate the entropy of an irreversible process to the external and internal properties, regardless of the energy content of the system. We can attain the same distribution of internal parameters imposed both reversibly and irreversibly by a set of external parameters. These different paths result in different work and energy changes in the system. However, we assume that a set of local parameters determines the entropy, and we can devise an ideal process that would reversibly bring the system to any configuration of the irreversible process. For example, diffusion of a substance is a nonequilibrium process, and the local concentration profile is necessary to define the system. We may apply reversibly a centrifugal field to the system to maintain the same concentration profile in a state of equilibrium. The energy applied reversibly to the centrifugal field is different from an irreversible diffusion process. Thus, the thermodynamic states of an irreversible diffusion process and the corresponding equilibrium system are different. Entropy may be computed as the corresponding entropy of the real system.

*Clausius statement of the second law is: It is not possible to construct a device that operates in a cycle and whose sole effect is to transfer heat from a colder body to a hotter body. *

The first and second laws are local laws to be valid regardless of the observer’s mobility and to be compatible with the principle relativity (**Kondepudi and Prigogine, 1999). **

Entropy is a state function. Its foundation is macroscopic and directly related to macroscopic changes. Such changes are mostly irreversible and time asymmetric. Contrary to this, the laws of classical and quantum mechanics are time symmetric, so that a change between states 1 and 2 is reversible. On the other hand, macroscopic and microscopic changes are related in a way that, for example, an irreversible change of heat flow is a direct consequence of the collision of particles that is described by the laws of mechanics. Boltzmann showed that the entropy of a macroscopic state is proportional to the number of configurations Ω of microscopic states a system can have

**(1.27) **

where *k*B is the Boltzmann constant (*k*B = 1.3805 × 10−23 J/K).

Consider a system with two chambers containing a total number of particles of *N*. The total number of possibilities for distributing the particles between the two chambers is Ω, which is the total number of distinct microstates with *N*1 number of particles in chamber 1 and *N*2 number of particles in chamber 2

Equation **(1.27) shows that disorganization and randomness increase entropy, while organization and ordering decrease it, and equilibrium states have the maximum value of Ω. In the above system, Ω reaches its maximum value when N1 = N2. In parallel, the increase in entropy corresponds to the increase in the number of microscopic states or states with higher probability. **

Balance equations consist of conserved, such as mass and energy, and nonconserved, such as entropy, properties. The following sections summarize the general balance equations of mass, energy, and entropy.

In an open system, mass flow rate for the flowing streams through the boundary is

**(1.28) **

where *v *is the average velocity, *a *is the cross-sectional area, and *ρ *is the density. Assuming that the flow is positive when it enters into the control volume and using Eqn **(1.28), the mass balance is **

This form of mass balance is also called the continuity equation. At steady state, the accumulation term (*dm*/*dt*) becomes zero, and we have

, where *z *is the elevation above a datum level, and *g *of all the entering and leaving streams in terms of the product of the pressure and volumes of each stream, we have a total energy associated with a stream *i *defined by

Using the equation above, we have a compact form of energy balance

are heat transfer rate and shaft work. The equation above assumes that the center of mass of the control volume is stationary. If the kinetic and potential energy changes are small enough, then Eqn **(1.30) reduces to **

The equation above is widely applicable to many thermal engineering systems. If a system is at steady state, then the accumulation term vanishes

or

A steam turbine operates with a steam flow rate of 3 kg/s. At the inlet, the steam is at 300 °C, 5800 kPa, and 32 m/s. At the outlet, the steam is saturated at 99.6 °C, 100 kPa, and 75 m/s. Heat loss is 30 kJ/s. Estimate the power produced by the steam turbine and compare with the power produced when the steam power production is carried out at reversible conditions.

Assume that the turbine operates at steady state and potential energy effects are negligible.

Data from **Appendix D: **

, *T*1 = 300 °C, *P*1 = 5800 kPa, *v*1 = 32 m/s, *H*1 = 2893.5 kJ/kg, *S*1 = 6.0969 kJ/(kg K)

Out: *T*2 = 99.6 °C, *P*2 = 100 kPa, *v*2 = 75 m/s,

*H*2V = 2675.4 kJ/kg, *S*2V = 7.3598 kJ/(kg K), *H*2L = 417.5 kJ/kg, *S*2L = 1.3027 kJ/(kg K)

*H*2V and *H*2L are the enthalpies at saturated vapor and saturated liquid states, respectively.

and *S*2 = *S*1 = 6.0969 kJ/(kg K). Since *S*2V > *S*1 the steam discharged is saturated wet steam with the quality *x *that is the mass ratio of vapor to the total mass of the discharged steam:

The rate form of entropy balances for closed and open systems are

is the rate of entropy production, which is positive for all irreversible processes and zero for reversible processes. Eqns **(1.32) and (1.33) are usually known as the second law of thermodynamics. Some properties of entropy change are: **

• At steady state conditions *dS/dt* = 0;

;

• For open systems going from state 1 to state 2 over the times interval of *t*1 to *t*2

, where *d*i*Sj *is the entropy production in the *j*≥ 0 for every *j*. This is valid for all systems at any boundary conditions.

In continuous systems, the local increase in entropy can be defined by using the entropy density *s*(*x*,*t*and results from the flow of entropy due to exchanges with surroundings (*d*e*s*) and from the changes inside the system (*d*i*s*). Therefore, the local entropy production can be defined by

**(1.34) **

The volumetric rate of entropy production becomes

The entropy of a system is an extensive property, and it changes through the exchange of mass and energy. If a system consists of several processes, the total entropy change is equal to the sum of the entropy changes in each process.

**(1.35) **

The value of *d*i*S *is zero when the change inside the system is reversible, and it is positive when the change is irreversible

In every macroscopic region of the system, the entropy production of irreversible processes is positive. A macroscopic region contains enough molecules for microscopic fluctuations to be negligible. When interfacial phenomena are considered, the entropy production is based per unit of surface area.

**(1.37) **

When the *T *is the environmental temperature, the dissipation function represents the local energy dissipated to the environment. The entropy production and the dissipation function are not state functions and depend on the path between the given states.

The work lost due to the rate of entropy production is

where *To *is the reference temperature, which may be the temperature of the environment.

Derive an expression for the entropy production for a system consisting of two closed subsystems of I and II.

Equation **can be applied to various irreversible processes. Let us consider a system consisting of two closed subsystems of I and II, and maintained at uniform temperatures of TI and TII, respectively. The total entropy dS is expressed as **

**(a) **

The interactions of heat in each subsystem are given by

**(b) **

Using **, Eqn (a) yields **

The entropy production per unit time is

**(c) **

Equation **. **

Derive an expression for the entropy production for a chemical reaction in a closed system.

Assume that the reaction is a single elementary reaction and homogenous.

Entropy change due to a chemical reaction in a closed system is given by

**(a) **

where *A *, *νj *the stoichiometric coefficient of species *j*, and *ε *the extent of the reaction.

Equation **. Therefore, the rate of entropy production can be expressed in terms of the rate of reaction Jr **

**(b) **

The equation above relates the entropy production to the product of the flows (here the rate of reaction) and the scalar thermodynamic force that is *A/T*, and can be readily extended to several chemical reactions taking place inside the system as below:

. The entropy production σ is:

Consider the following two mixing processes:

Mixing process 1: In a steady mixing process, 14.636 kg/s of saturated steam (stream 1) at 133.9 kPa is mixed with 15.0 kg/s of saturated steam (stream 2) at 476 kPa.

Mixing process 2: In a steady mixing process, 11.949 kg/s of superheated steam (stream 1) at 773.15 K and 6000.0 kPa is mixed with 60.60 kg/s of saturated steam (stream 2) at 2319.8 kPa. The product stream is at 523.15 K. Assume that the mixing processes are adiabatic.

Determine and compare the rate of entropy production and the lost work for these two mixing processes producing a product of stream 3.

Assume that the surroundings are at 298.15 K and the kinetic and potential energy changes are negligible.

Mixing process 1: Available data from the Steam Tables in **Appendix D are **

Assuming negligible kinetic and potential energy changes, mass, energy, and entropy balances yield:

From the steam table, we read: *T*3 = 401.15 K and *S*3 = 7.0462 kJ/(kg K)

:

becomes:

The dissipated work potential is small as

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