Contents Front Matter 1 1.Preface 2 2. Basie Relations and the First Law 4 3.The Second Law of Thermodynamics. 42 4. Availabilty Analysis. 68 5. Availablity Analysis of Cycles 134 6. Equations of State 162 7.Thermodynamie Property Relations 192 8.The Third Law of Thermodynamics 246 9. Thermodynamic Properties of Homogeneous Mixtures 326 10. Multiphase-Multicomponent Systems 379 V1.Chcinival Resutions 429 12.Chemical Availability 485 13. Chemical Availability of Fuels 50% 14.A Statistical Viewpoint of Entropy 527 Back Matter 535 15, Appendix A: Supplementary Tables and Figures 546 16. Appendix B: Symbols. 610 V7.Index. 615Credits Front Matter 1. Preface: Chapter hom Advanced Thermodynamic for Fagiower hy Wark > 2. Basie Relations and the First Law: Chopter! from Advanced Thermodynamic for Engineers by Work 3. The Second Law of Thermodynamies: Chapter? rom Advanced Thermodynomies fr Engineers by Work 42 4. Availability Analysis: Chapter from Advanced Thermodynamics for Engineers by Wark 83 5. Availability Analysis of Cycles: Chapter from Advanced Thermadynamves for Engineers by Wark 124 6. Equations of State: Chapter Som Advanced Thermodynamics for Engincesby Wark 162 7. Thermodynamic Property Relations: chapters hem Advanced Thermodynamics for Engineers by Wark 192 8B. The Third Law of Thermodynamics: Chapter from Advanced Thermadynamicsfor Engineers by Wark 246 9. Thermodynamic Properties of Homogencous Mixtures: Chapter 8 from Advanced Thermodynamics for Engineers by Work 326 10, Multiphaco Multicomponent Systems: Chapter 9frem Advanced Thermodynamics for Engineer by Wark 370 11. Chemical Reactions: Chapter 10 from Advanced Thermodynamic or Engineers by Wark 429 12. Chemical Availability: Chapter 11 fiom Advanced Thermodynamics for Engineers by Wark 485 13. Chemical Availability of Fucls: Chapter 12 rom Advanced Thermedynamcsfor Engineers by Wark 501 14.4 Statistical Viewpoint of Entropy: Chapter 13 from Advanced Thermodynamics for Engineers by Wark S27 Back Matter 515 15. Appendix A: Supplementary Tables and Figures: Chapter from Advanced Thermodynamics for Engineers by Wark 546 To. Appenuix B: Symbols: Chaprer rom Aawanced Thermacynamics fr Engineers by Wark 910 17 Index: Chapter hem Advanced Thermodynamics fr Engineers by Wark 615Front MatterAdvanced Thermals PREFACE ‘This textbook is the outgrowth of teaching a senior-graduate-evel course in ther- ‘modynamics at Purdue University over the past 25 years. Other instructors have shared this particular teaching responsibility, and | am indebted to them for the ‘numerous discussions on the theory and practice of thermodynamics on all levels. (Over this time period we have used many different texts, few of which are still in print. As a result, the need for hand-out notes for the course increased over recent years. The text evolved from these notes In theie final form all chapters hhave been class tested several times, while some have been in use over the past three to four years. Student feedback has been invaluable. Engineering graduate students have varied backgrounds, including some with nonengineering undergraduate degrees. Hence the first two chapters are used to review and extend basic frst- and second-law concepts. Special attention is given to the role of entropy production in nonreactive processes. With national attention ‘on energy usage, the third and fourth chapters discuss the theory and application of availability (or exergy) concepts to nonreactive processes and cycles. Chapters 5 land 6 present the theory and experimental correlations for the important properties of simple compressible substances. Emphasis is directed toward the use of PoT ‘equations of state in the evaluation of other properties inthe single- and two-phase regions. Chapter 7 is a short discourse on the third law, modeling of specific-heat data, and experimental work in this area. Chapter § covers the general theory fof multicomponent, single-phase systems, including the concepts of a partial ‘molal property and the chemical potential. Chapter 9 extends this discussion to multiphase, multicomponent systems. General coverage of the first- and second-liw applications 1 reacting systems i presented in Chapter 10. The affinity of system is introduced as a means for determining the direction of change for a chemical reaction. In addition, a comparison af real- versus ideal-gasAdvanced Thermodynamis for Engineers xvi reerace eswilibrium is presented. A major topic inthis chapter isthe availability analysis of reactive systems with respect toa restricted dead state. Chapter 11 introduces chemical availability and the envigonmental dead state for reactive systems, and Chapter 12 deals with the chemical availabilty of fuels andthe concept of the standard chemical availabilty. Chapter 13 provides insight into the microscopic or molecular origins of the entropy function, heat and work, and the second law ‘of thermodynamics, This chapter could easly be assigned in conjupetion with Chapter 2. ‘As at aid in course planning, some comments on time allotment to vatious chapters may be helpful. I is dificult to predict the class time to spend! on the frst two chapters. Insructors, however, may fee! it prudent o spend considerable time in the review and expansion of Basic concepts, especially with respect to the second law. For the remaining chapters, based on class experience, the author suggests thatthe following minimum class period allotment may be appropriate: Chapter 304567 8 9 WU 12 Periods 4-5 326 3.5667 6 1 3 ‘The time to spend on microscopic aspects of entropy and the second law is also ‘one of personal judgment. The course for which this text was written has always been directed toward engineering applications and problem-solving techniques. To this end the text contains nearly 400 problems which cover all major subject matter. Most of these problems deal with the engineering aspects of process and cyclo analysis. All the [pmhleme ar expressed ia SI unite. ‘The only exception is the use of wither 1 atm fo 1 bar as a standard reference pressure. The use of a personal computer is appro- priate for problem solving in a number of eases, Polynomial curve fitting of data {and the solution of cubic equations are two examples, as well asthe use of a data plotter. A software package which contains both files of thermodynamic data and ‘equation-solving techniques also is quite useful. Some problems in Chapter 10 re- ‘quire data from the JANAF tables. Examples ofthese tables are not provided in the Appendix, but the unabridged tables are readily available in engineering libraries. Instructors may wish to provide tables for a few basic substances to theit classe. A solution manual, which is detailed and complete, is available. In addition to the helpful comments from students, am indebted to Janice Napier and Kathy Taylor, ‘who expertly typed a large portion of the original manuseript. | would also li thank the following reviewers for their many helpful comments and suggestion Robert Balmer, University of Wisconsin; Eugene Brown, Virginia Tech Univer- sity; Baki M. Cetegen, University of Connecticut; Creighton Depew, University ‘of Washington; John R, Lloyd, Michigan State University; Mohamad Metghalehi, Northeastem University; Michacl Moran, Ohio State University: Henry Petkins, University of Arizona; G. P Peterson, Texas A&M University: Ramendra Roy, Asizona State University, J. D. A. Walker, Leth University; and James Welty, Oregon State University. Kenneth Wark, Jr.Advanced Thermals CHAPTER 1 BASIC RELATIONS AND THE FIRST LAW ‘This chapter reviews the basic concepts of thermodynamics and discusses the pplication of the general energy balance to transient systems. 1-1 REVIEW OF PROPERTY EVALUATION AND BASIC LAWS ‘This section begins with a review of basic definitions, followed by a convenient summary of equations and procedures for evaluation of thermodynamic properties for simple compressible substances (ideal gases and incompressible liquids) and, Where tables are available, for materials of more complex behavior. In addition, some basic relationships for the fir and second laws are reviewed. However, this section does not develop or examine theory in detail, For more information see ‘any basic engineering thermodynamic text. 1-1-1 Basic Terminology ‘Any thermodynamic analysis begins with the precise specification of the matter or space under investigation. A thermodynamic system is a three-dimensional region of space which is bounded by an arbitrary surface. The control surface or bound- ‘ary may be teal or imaginary, may be at rest or in motion, and may change its size fot shape. Difficulties frequently arise when systems are not adequately denines before an analysis is begun. A system could be as simple as the matter within a 1Advanced Thermodynamis for Engineers 2 paste RBLaTIONS AND THE FIRST LAW piston-cylinder device, oF as complex 2s portions of an oil refinery. All physical space which lies outside the arbitrarily selected boundary of a system is called the surroundings or environment. An important characteristic of a boundary is that it neither contains matter nor occupies a volume in space. Hence the thickness of a boundary is mathematically zero and a property value at « point on the boundary is shared by both the system and the local envionment. ‘The analysis of thermodynamic processes includes the study of miss and energy transfer across the boundaries. A closed system ot conirol-mass analy- sis involves no mass transfer across the boundaries, However, energy transfer is allowed, as well as a change in chemical composition within the system, Con- versely, mass and energy may cross the boundary of an open (flow) system, which is also called a conirot volume. ‘Tie systeun itself fs Uescribed by Its properties, These are macroscopic ehar- acteristics to which « numerical value can be assigned without knowledge of the history of the system. ‘The origins of properties include those (1) directly mea ‘surable, (2) defined by laws of thermodynamics, and (3) defined by mathematical ‘combinations of other properties. The descnption of the condition of a system at 4 given instant is known as the stave of the system. A state can be completely identified from a small subset of (independent) property values. The values of all remaining (Jependent) properties can be determined in terms of the subset Properties are defined only when a system is in equilibrium, Any transformation of @ system from one equilibrium state to another (the end states) is called a process. The path of a process is the series of states through which the system passes. When a system is infinitesimally close to equilibrium at all times ducing process, the process is called quasistatic. A complete description of a process requires specification of the end slates, the path, and the interactions across its bboundacies, When a system undergoes @ change in state, the change in the value of a property does not depend on the process connecting the two end states, Hence the change in value of a property is fixed only by the end states. Conversely, if the value of a quantity is independent of the process between two end states, then that quantity is the change in a property. If the value of a quantity depends on the nature of the process between two end states, the quantity is not a property Examples of this latter quantity are heat, work. and mass interactions, as well 4s entropy production and iereversibilty. (These latter two items are discussed in detail in the next two chapters.) Properties are classified as either extensive or intensive. Extensive properties depend on the size ofthe system, Examples include ‘mass, volume, and energy. The values of intensive properties are independent of the size of the system, such as pressure andl temperature, However, they may Vary in value with both position and time. When an extensive property value is divided by the mass of the system, the resulting property value per unit mass is called a specific property. A specific property is an intensive property. A phase of a system 's the collection of all regions af the system thar have the came intensive state and chemical composition,Advanced Thermals [REVIEW OF PROPERTY VALUATION AND HASIC LAWS 3 ‘A further classification of properties frequently is made in terms of intrinsic ‘and extrinsic characteristics. In general, for any system: L. An extrinsic quantity is @ quantity whose value is independent of the nature ‘of the substance within the system boundaries. 2. An intrinsic quantity is a quamtity whose value is dependent on the nature of ‘the substance composing the system. ‘These terms, for example, can be used with respect to propertics of a system. Examples of extrinsic properties include translational velocity, rotational energy, and clectric field strength. Intrinsic properties include temperature, pressure, and internal energy. 1-1-2 Conservation of Energy Principles ‘The conservation of energy principle for a closed system is O+Ww=ae (1) where Q and W represent heat and work interactions, respectively, and £ repre= sents all forms of energy. Consider a closed system which undergoes a cycle, for which AE is zero. This system is a perpetual motion machine of the first kind (a PMM1) if no other external effect occurs other than net work output, ot if the net ‘work output is greater than the net heat input. A simple compressible substance is one for which the only relevant reversible (quasistatic) work mode is boundary ‘work. For a simple compressible system which is stationary the energy balance for the control mass becomes Q+w=au a2) ‘where U is the intrinsic internal energy of the substance. The quantity W may represent several forms of work which may be present during a specified process. (On a unit-mass basis the above equation becomes. qtw= Au 3) In the above equations the heat Q (or q) and the work W (or w) are taken as positive when they occur into the system. For the steady-state flow of a simple compressible fluid throagh a control volume (CV) the conservation of energy is frequently written in two formats. On a rate basis, OrW- Salie See) Sali Soe) oo and on 6 uuittainss basis for a vontiol volwme with one inlet (1) and one out let 2),Advanced Thermodynamis for Engineers 4 susie mELATIONS AND THE FUSE Law va z ete =n m9+(4 Das) where w usually represents any shaft work present, the specific enthalpy = 4+ Pe, and a(~ pAV) is the mass flow rate at a given pesition, 1-1-3 Second-Law Relations ‘A fundamental relationship relating the entropy change of a control mass (closed system) to the heat interactions that occur is as > 22 a8) T where the inequality applies to internally irreversible processes and the equality o imtecnally reversible processes, The equation assumes a uniform temperature at the system boundary. The above inequality can be written as an equality by including a term or, which represents the contribution to the entropy change duc to the presence of internal imeversibilities. Thus the above equation is frequently written as = 2,4 : as = 2 an sihereo = 0. For itemlly reversible processes 80/ is ety rested to the as = [*(f2) as Heat reservoirs are closed systems which are defined as internally reversible and of constant temperature, For such systems the above equstion reduces to AS = Q/T. The relationship for dS leads to evo well-known forms of the increase in entropy principle, AS yin = 0 and — dS = 0 a9) ‘Thus for adiabatic or isolated systems the entropy always inereases in the presence of inreversibilites, or in the limit of reversible processes the entropy change is 7e10, 1-1-4 Property Considerations of a Simple Compressible Substance AAs noted earlier, a simple compressible substance is one for which the only rel- vant, intrinsic, reversible work mode is boundary (P dV) work. On the basis of the state postulate the number of independent, intensive, intrinsic propertiesAdvanced Thermals -REVICW OF PROPERTY EVALUATION AND BASIC LAWS S required to fix the state of such a substance is two. In general, any two may be chosen as long as they are independent of one another (In certain eases one property may be a function of only one other property and these two cannot be chosen a the independent variables.) In addition to P, T, and ©, we shall be concerned with the properties w (Goternal energy), hh = 1+ Pe (cathalpy),s (entropy), a = 1 ~ Ts (Helmholtz function), g = A ~ Ts (Gibbs function), and two specific heats: on) mw =) 10) A combination of the first law in the form 5q + 5 ~ die, the restriction that ‘Bw = —P de, and the defining equation ds = 8q/T leads tothe T ds equations. ‘The T ds equations provide the basis for property relations. Two important forms are Tds=du+Pdo and fds = dh —vdp aay I-15 Ideal Gases ‘The basic equations applying to all ideal gases are Po=RT cp-co=R k= a2 dh = cyd? du = cedT a) aT dP oe Tg lt : eR asm Ke ona [Note that hand u are functions of T only but that sis a function of two variables. 1-1-6 Ideal Gases with Constant Specific Heats In general, cp and cy are functions of T only for an ideal gas. For some gases (such as the monatomic gases He and Ar) the specific heats are constant over large temperature ranges. For many other gases cp and c change slowly and often can be taken to be constant over limited temperature ranges, If ¢p and ce are taken to be constant, the expressions for dh, du, and ds can be easily integrated. The results are hy— hy eT2-T) and wa m= eK N)— (145) wE-emtoqme+enZ 19 en Pi aos “The (senrropic process, where 5 is a coustant, iy au iampurtant one. Whee 51. the two expressions above can be manipulated to giveAdvanced Thermodynamis for Engineers 6 axsie RaLATIONS AND THE FIST LAW Aer" -er" = | 1-1-7 Ideal Gases with Variable Specific Heats and the Gas Tables The gas tables (such as those by Keenan, Chao, and Kaye) enable one to ac- ‘count for variable specific heats by tabulating those integrals which are tedious or difficult to evaluate. Enthalpy and internal energy are calculated from ‘where equations for cp and ¢, a8 a function of temperature must be known, (Note that in these tables Irgy and ine are arbitrarily asrighed the value zero at Tig ~ 0.) ‘Thus Ak and Aw are found directly from the table as the difference between wo values at the given two temperatures. The entropy evaluation is written as Py Te aos = f-sp- Rin s ar 11 venedednem mg [Zar aay ‘The s° values are tabulated solely as a function of temperature. In a constant ‘entropy process in? Gaon a, ‘The gas tables sometimes also provide a somewhat more convenient scheme for isentropic processes. A quantity p, is defined as 5 = X np, (So p, is a function of T only). When s2 = s1, then 52 Gsentropic) (1-20) ‘The values of p, and v, are tabulated along with k, u, and s° as a function of temperature in some tables. 1-1-8 Incompressible Materials Many tigi and solids, lest ver Hite temperate ranges, ae uit in terlve to reste. Their behavior canbe eppotraled ye const. The consequences a tat eptene dunedt, dhwedt+odp, ad dee Sat aanAdvanced Thermals REVIEW OF PROPERTY EVALUKTION AND BASIC LAWS 7 Ihe is assumed constant uu) = P21) hy = c-T)+(P)—P)) (1-22) h and mos =eln - nF (1-23) 1-1-9 Standard Tables of Properties ‘These tables are used particularly if the substance in question may exist as either liquid or vapor in the region of interest. Remember that for mixtures of liquid and vapor T depends only on P. The saturated-liquid and saturated-vapor properties are functions of P or T-. Properties of mixtures are weighted average values. The quality x is defined ws mass of vapor ‘ase of mixture Theretore hahptihy wus tug Sat xs 0 Of xO, where ¥ 7 u=h-Po. If the substance is supetheated vapor, the properties v, ht, s (and sometimes. 10) are tabulated as functions of T and P. Only a few tables (notably H;0) include the compressed liquid region, where the pressure is greater than the saturation pressure atthe given temperature. Properties are presented in the same way as for ‘superheated vapor. Since most tables do not include compressed liquid data, it may be necessary to estimate these properties. This can be done by treating the ‘compressed liquid as an incompressible material so far as pressure is concerned. For such a liquid u, ©, and 5 are independent of pressure so that saturated-liquid values (at the same temperature) may be used. To evaluate the enthalpy, ome uses dh = cdT +04P. Let +h = enthalpy of compressed liquid at P and 7 ‘hy = enthalpy of saturated liquid at Pay, and T voy = specific volume of saturated liquid at Pa and T ‘Then h = hy + 0f(P ~ Pax) ‘yp ~¥4- In some tables no intemal energy values are given. Use 11-10 Adiabatic (First-Law) Efficiencies The actual flow through many engineering devices is approximately adiabatic. (One method of estimating the imeversible performance of an adiabatic device isto ‘compare it to the isentropic performance. This type of comparison is expressed in a pirameter known as the adiubutic, isentropic, or fis-law efctency ofthe device. ‘The comparison is made for the same inital state and the same final pressure.Advanced Thermodynamis for Engineers 8 sAste RELATIONS AND THE FIRST LAW ‘Such efficiencies are applicable to systems such as turbines, compressors, pumps, ‘and nozzles, Use of the subscripts “a” ands” to represent the actual and isentropic flows, and 1 and 2 t0 represent the inlet and outlet states, respectively, leads to the definitions of the various efficiencies noted below. ‘TURBINE EFFICIENCY. The turbine efficiency 1 is the ratio of the actual work {0 power) to the isentropic work: that is, Wa Wa hy hae We We the ny (turbine) (1-24) where the approximation sign applies when the kinetic-energy change across the Imrhine is mgligible Turhine efficiencies generally range from $0 to 90 percent NOZZLE EFFICIENCY. The nozzle efficiency my is the ratio ofthe actual kinetic- ‘energy change to the icentropic Kinetic-energy change. In mony easee one can reazonably neglect the inlet kinetic energy in both cases. Thus for # norile where Ake = Ah Vig/2 = V9/2 _ ty = how V/2—Vi/2 I= hay ™ = (nore) (1-25) Nozzle efficiencies usually range upward from 90 percent COMPRESSOR EFFICIENCY. The compressor efficiency 1. is defined as the sitio of the isentropic work (or power) to the actual work. That is, (compressor) (1-26) ‘where the approximation is valid when kinetic-energy changes may be neglected. Compressor efficiencies typically range from 70 to 85 percent. PUMP EFFICIENCY. The pump efficiency , is defined similarly to that of a ‘compressor. Beat um azn Where the approximation holds when Ake is negligible, Pump efficiencies range From 50 to 90 percent, 1-2. FIRST LAW FOR CLOSED SYSTEMS. ‘The conservation of energy principle enunciated in Sec. 1-1-2 for closed systems sfates that Q+W~ ar ayAdvanced Thermals fons Law For evosep sysnins 9 Historically the above equation has been atsived at by wo different starting points. These two viewpoints can be traced to Poincaré [1] and Carathéodory [2]. A lengthy discussion of the historical development of the frst and second laws appears in Bejan (3). These two approaches ae summarized below. The methods ~ £1. By definition, the value of the heat interaction during such a change of state is given by 80 = dE ~ BW = BWyn ~ BW 1-29) For a finite change of state this equation takes the expected form of Bq. (1-1). In addition, when heat transfer is zero hetween two systems separated by a non- adiabatic wall, the two systems are defined to be of equal temperature. Heat is energy in transition which occurs by virtue of a temperature difference. 1-2-2 Poincaré’s Approach A second approach to a first-law statement and a mathematical formulation of a conservation of energy principle ist select heat, work, and temperature as primary concepts. This requires that the concepts of heat and work be defined jously. The experimental foundation for the first law in this case is the “mechanical equivalent of heat” measurements by Joule in the 1840s, and by others. A system is altered from a given inital state to a specified final state either solely by a work effect or a heat interaction. It is found that the quantity of heat required is proportional to the work required, (This proportionality, rather than equality, was due to Q and W being measured in different units in the ‘midnineteenth century.) When the state is altered solely by a work effect and a heat effect is used to return the system to its initial state, the same proportionality between Q und W is observed. This type of data leads to the conclusion that ‘when a system undergoes a cyclic process, the sum of the work transfer and the heat transfer for the complete eyele is zor. The mathematical formulation is $8044 aw This is the Poincaré formulation of the fit law. AS a final step toward a cooser- vation of energy principle, the above relation is applied to two cyelic processes berween states | and 2 of a closed system, The Hirst eyele consists of path A from {to 2 and path € from 201. A second eycle consists ofa differen pa B from | to 2 butte same path C trom 2 to 1. For those to eyes Eq, (1-30) becomes [eee] J 600+ [!s00+ "om + [ome ‘When the second equation is subtracted from the first equation and the result is rearranged, we find that (1-30) 80c+ fi Ws +f We = 0 0 [00 + 5H), = [60 + ¥»Advanced Thermals Because processes A and B between end states | and 2 are completely arbitrary, the quantity (6Q + BW) must be the same for all paths between states 1 and 2. ‘Therefore the value of this quantity is independent of the path and depends only ‘on the initial and final states. Thus the quantity (6Q + 6W) is a measure of the differential change in a property. By definition, then, 60 +8W =dE and we have arrived at the same conservation of energy principle for clased systems as developed by the Carathéodory approach Thus both the Carathéodory and Poincaré approaches, although based oa different empirical data, contain two related results: (1) the existence of an en- ergy function and (2) the mathematical formulation of a conservation of energy Principle fora closed system. Either approach has its adherents. The development of Carthéodory’s scheme has the advantage that heat transfer, and the standant- ization of its measurement, is nota primary conce 1-3 ALLOWED STATES One method of classifying interactions as either heat or work is based on the concept of allowed states, and is due to Hatsopoulos and Keenan [6]. By their definition, the allowed staves of a system are all the states which the system ‘ean assume consistent with (1) the laws of matter, (2) passive resistances, and ) constraints. The laws of matter include the: 1. Law of continuity 2. Law of conservation of charge 3. Law of conservation of chemical species Passive resistances are those internal constraints which prevent the attainment Of certain equilibrium states which otherwise might be expected. A short list of ‘examples might include: 1, Impermeable walls, which prevent the passage of matter from one region of the system to another region 2. Adiabatic walls, which prevent the exchange of heat from one part of the system to another part 43. Solid friction, which might prevent the movement of one part of a system relative to another part 4. Amticaalysts, which prevent a change in chemical composition The removal ofa passive resistance constitutes a change in the nature of a system and alters the total numberof states posible. Finally, constraints ae thoce ro strctions imposed by the environment on the states that a system might assume. They include one of more of the followingAdvanced Thermodynamis for Engineers 12 easie waLanions ano THe Fs LaW” A. An upper limit of volume 2. A conservative force field established by bodies in the em 3. An electrically insulating wall, which prevents the flow of ele the system and its environment “The above conditions establish the states in which a system might be found, that is, the “allowed states.” Consider two systems initially in equilibrium. A general characteristic of all ‘work interactions is that at least one of the two interacting systems is not in an equilibrium state, To place a system into nonequilibrium requires that a passive resistance or constraint must be altered, which in tum alters the number of allowed states of that system. Hence: ‘Any work interaction requires an alteration in the allowed states, On the other hand, a heat interaction only requires that two systems initially im equilibrium be brought into thermal communication: Any heat xaction does not require an alteration in the allowed states ‘Thus there is a significant difference between feat and work interactions when ‘expressed in terms of the allowed states of the interacting systems. In Chap. 2 another differentiation between heat and work will be noted based on entropy tuansfer across a boundary. 1-4 UNCOUPLED AND COUPLED SYSTEMS ‘A. major thrust of engineering thermodynamics is toward the study of eneray conversion devices. These devices generally fall into two categories: (1) work input to work output and (2) beat input to work output. In either case the enerzy conversion device falls imo a class called coupled systems, Blememts of systems which are uncoupled do not lend themselves to input-output conversion devices. ‘Thus the differentiation between coupled and uncoupled interactions is of some importance. 1-4-1 Uncoupled Systems In an tmcoupled system each type of interaction (work or heat) leads to the change ina form of energy storage unique to that interaction. An uncoupled energy system. is easily explained by writing the conservation of energy principle for a closed system in the following format: + Wy + We te = AU + AE) + AEs + ‘For an uncoupled system the value of J equals AU, Wy equals tne vatue oF AE\, Ws equals the value of AE>, and so forth. Thus not only are the interactionsAdvanced Thermals uncourtsp axp courte svstiass 13 separate, but the energy stonige modes they affect are separate. As a simple physical example. consider an incompressible block of mass m and specific heat ¢ initially at position zy, velocity Vj, and temperature T;. By heat and nondissipative work interactions its final state is (ca, ¥3, 72). For the overall process Q = me(Tz-Ty) Wy = AE = m(V}-VP/2 We = AE; mg ‘These are familiar concepts and equations. ‘The major point is that separate system behavior (in terms of energy storage) is associated with each type of interaction. The heat interaction does not affect V or z, Thal is, we do not expect ‘2 heat addition to result in either an increase in translational kinetic or gravitational potential energy. Table 1-1 lists some examples of uncoupled forms of work. In the Ideal shustion the velocity and elevation changes discussed above ‘could be reversed. The work interactions for the reversed progress would be ‘equal in magnitude but opposite in directions compared to the original process. When work 1s completely recoverable during a cycle, the system is known as a conservative system. Mathematically this requires that fow=0 ma fao-o for uncoupled systems. [The cyclic heat relation above is required by Eq. (1-30). In actual systems we know that dissipative (frictional) effects of various kinds are present. As a result, work is not recoverable during such a cyclic process, and the system is said to be nonconservative. A major characteristic of systems undergoing a cyclic process with dissipative effects present is that the net work is always positive (into the system). On the basis of the conservation of energy, then, the net heat transfer must be negative (out of the system) for the cycle. TABLE LL Some common examples of uncoupled forms of work and energy storage Force displacement Macroscopic Energy storage form elation Work trate, 6W energy storage Kine, ranslational Fama Fas 7 Kinetic, ational rele +a fo 0b) otemial, gravitons rome Fade mmsiea 2) cca, capacitance t-% 0 20-02) lec, indutance eg & ae. haa) Poem eletrostae “se}- ep Potent, megoetostne 01)Advanced Thermodynamis for Engineers 14 asic meLATIONS AND TH FIRST LAW 1-4-2 Coupled Systems Unlike uncoupled systems, the coupling of eneray interactions is said to occur ‘when two or more interactions affect the same mode of energy storage. OF primary importance for engineering applications are coupled systems in which the internal ‘enorgy U is affected by both heat and work interactions. In such cases separate energy storage modes are not altsibuted to the separate thermal and work effets AAs a result, both @ and W affect the same thermodynamic properties of the system. In fact, « heat effect or work effect alone will change both thermal and mechanical properties of a coupled system. Thus the thermal and mechanical properties themselves are coupled. Table 1-2 Fists some examples of coupled, ‘quasistatic forms of work. All energy conversion systems are examples of coupled behavior, Recall for uncoupled systems that faw Tn contrast, for heat-to-work converters it is desired to produce net work output by the cyelie device. Thus for such a coupled thermodynamic system undergoing. acyclic process + amt fo fve0 amt fo0e0 ean However, m order to satisty the conservation of energy principle, the sum of the two cyclic integrals above must equal zero [see Eq. (1-30)]. Thus the test for the TABLE 1-2 Examples of intrinsic, quasistatic, coupled-work interactions Generalized Generaoed “Type of work three, Fe Aaplacement, Xe Work equations Boundary a v ~Pav Spring x (= Lb) Pads nd ° « Vo de Capacitor of ‘hemical el « a 40 Surface y a yaa Toon : ° ae ete polarization E > ve-4P # “ Voll «datAdvanced Thermals coupling of two different energy interactions and their thermal and mechanical properties is: For at least one eycle exccuted by the system, in the absence of any dissi- ‘pative effects, the net value for each mode of energy transfer is nonzero, This generalization is exemplified by Eq. (1-31) for beat-to-work conversion de- vices. In heat engine design one should select a working fluid whose mechanical and thermal properties areas strongly coupled as possible, Fluids inthe gas phase {ull this requirement quite well. For example, at low pressure Po = RT. The thermal property (7) is strongly linked (coupled) to the mechanical properties (P and c). For this reason gases (Ideal or real) are widely used in heat engines, as exemplified by gas turbine (GI), spark ignition (St), and compression ignition (Ch engines. ‘Work interactions may be coupled to produce work-to-work conversion de- vices. An example is a parallel plate capacitor which undergoes both a change tn plate spacing and a change in charge. For this adiabatic, nondissipative device the energy equation becomes °. 2 Bro By = [edge + [rae (1-32) lees bs ‘The property (constituitive) relations for this system are given by Dex #0. _ OF woe MP eh where é Is the permitivity of fies space, 4 is the area of a plate, and F is the extemal force required to hold one plate in a fixed position. Note that the constitutive ations contain common terms, and hence are coupled. Thus the two ‘Work interactions are likewise coupled. A more complete discussion of uncoupled and coupled systems appears in Ref. [4]. 1-4-3 Intrinsic and Extrinsic Energies Another viewpoint of uncoupled versus coupled behavior is through the concepts of intrinsic versus extrinsic energy effects. (The general definitions of inti and extrinsic appear in Sec. 1-1.) The conservation of energy for a closed system, Eq. (1-1), can be expanded into the form 30 + 8W™ + BW = dE + dE (1-33) where the superscripts “ext” and “int” represent extrinsic and intrinsic forms, respectively, of work and energy. It is important to note that heat transfer affects ‘only the intrinsic state of a subotance, The total kinetic forms of energy include the macroscopic translational and rotational forms relative to the center of mass, asAdvanced Thermodynamis for Engineers ‘well asthe kis by energy of the particles within the system. They are represented Exes = Eine + Ege + UR where E = U for intrinsic stored energies. ‘The total potential energy includes the gravitational form, as well as those due to stationary and moving charges (electrostatic and magnetostatic). A fourth form isthe intrinsic potential energy of its particles within the system. These may be represented as Ercan = Egy + Eee + Eiing + URE ‘a Five of the seven listed forms of kinetic and potential energies are extrinsic and ‘measurable. The sum of the two remaining intrinsic terms Is defined as the internal energy U of the substance. It is not directly measurable but must be evaluated in terms of measured interactions or from expressions relating it to other measurable properties. Un the basis of the preceding discussion Eq. (1-38) becomes 6Q + 6W™" + Wi" = dU + AES, + dEg + ESS, + dESS + dE Sa, However, al the extrinsic forms of work (the quantity 81° is sum of terms) ane uncoupled on one-to-one basis with their comresponding dE** terms. Dropping cut the uncoupled terms, we find that 6g +5Wi = dU a3) ‘This is an intrinsic or coupled energy balance. Heat transfer and various forms of intrinsic work interactions together bring about a change in the intrinsic (molec- ular) energy U of the system. Thus the internal energy is defined, through the first law, in terms of coupled properties of the system. For example, for a simple ‘compressible sysiem the internal energy is usually expressed by a relationship of the type « = f(T, 0). The temperature T and specific volume v are thermal and ‘mechanical properties, respectively. ‘There are situations where systems are influenced by both uncoupled and coupled behavior, For example, consider @ coupled system which undergoes a change in elevation while also experiencing heat and intrinsic work effects. In this case the conservation of energy equation becomes O+W = AU +E gay where W includes the uncoupled work associated with the elevation change and the coupled intrinsic work. 1-5 GENERAL CONSERVATION OF ENERGY PRINCIPLE FOR A CONTROL VOLUME “The comeervatinn af energy principle may he applied to a eontmalsunhune analyeie by properly extending the energy equation developed in Sec. 1-2 for a control mas.Advanced Thermals CGestkaL CuNDERAnION UF ANNO Manca A CowTROL voue 17 1-5-1 General Considerations We shall consider the control volume shown enclosed within the dashed line in Fig. 1-1(@). The control surface at sections | and 2 is open to the transfer of mass in of out of the control volume. At some initial time + we focus our attention on the control mass. which is the sum of the mass within the control volume at that instant and the mass mq within the volume element marked A, which lies adjacent to section 1. At time ¢ + Ae this control mass has moved s0 that all the ‘mass originally in region A is now just inside the control volume. In the same time interval part of the control mass has been pushed out of the contral volume into the region marked B, which is adjacent to section 2 (Fig. 1-1(6)]. The mass and volume of regions A’and B are taken to be small compared to those of the Control volume. During the time interval Ar heat and work interactions may have ‘occured fo the control mass. AAn energy balance on the eomUOL HES is + W = Bou = Fowssar~ Eour 35) Since the masses associated with regions A and B are small, compared to the ‘control volume, the heat and work effects on the control mass are essentially the same as those Which cross the boundary of the control volume. ‘The right-hand side of Eg. (1-35) may be expressed in terms of the control volume in the following manner: The energy E of the control mass at time # is the sum of the energies of the mass within the contol volume at that instant plus the energy of the mass in region A. This may be expressed 98, Eows = Eev.s + Ein @ ‘where the subscripts again indicate the physical significance of the terms and ME is the increment of energy associated with the mass which passes from region A imo the control volume. In a similar fashion, the energy of the control mass at time ¢-+ Ar would be Eewsea = Eeveoas * ME we o ” » FIGURE 11 ‘The development of conservation principles fo a corol-volume analysis (2) Conta rs atm ¢ (2) com massa ime t+ ArAdvanced Thermodynamis for Engineers 18 se ens An HS LA ‘The quantity AFau is the increment of energy associated with the mass which ‘asses from the control volume into region B. Subtracting Eq. (b) from Ea. (a), ‘we find that Beatuear ~ Bonus ~ (Ecy.evar ~ Bey) ~ Akin + MEou © ‘The left-hand side of Eq. (c) is equal to the right-hand side of Eq. (1-35), Sub- stitution of Eq. (¢) into Eq. (1-35) yields OW = Eevasar ~ Eevs ~ Min + ME vt @ ‘The conservation of energy principle for a control volume is now placed on 8 rate basis by dividing Eq. (4) by the time interval A. Hence OW _ Eovssys~Eevs _ AFin , MEou ® Ota ar ae Se ‘The limit is now taken as Ar approaches zero so that each term may be expressed as a derivative, As a result, 5p dev _ dln , dow OW a a where 60/d1 = 0 and 8W/dt = W. @ isthe instantaneous rte of eat transfer to the control volume, and W is the ate of work done on the system, oF the power. A tis point it is desirable to change the last two quantities in Eq. (1-36) to terms identifiable with the mass crossing the contol surface. Because the mass in region A would be differentially small fora time interval dt, this small mass hich ties adjacent to section I would have the thermodynamic properties as- sociated with that particular section if the condition of local equ valid. Consequently, Eig = ei, o€ dBq/de = ey(dmy/d. A similar exprese sion holds fr the transpor of energy at section 2. Further dm dis defined a the mass flow rate rt Thus dEg/d1 = gin and dEgy/ di = eau. Substitution ofthese two expressions into Eq, (1-36) leads to (1-36) OW EO cin + coat (137) ‘The energy ¢ represents all forms of conceivable energy tha might be associated with a unit of mass, Finally, the work term in Eq, (1-37) must be separated into three parts. The first ofthese isthe flow or displacement work associated with mas crossing a con- trol surface. The work 8W necessary to push a differential mass Bm into a contol volume is the product of the force PA and the distance V dr under uniform flow, or PAV dt. Recalling that = pAV, we find that 8Wayy = Peri dt or ona ate buasis, Wage = Pert. Secondly, we must consider shaft work Which is measured by devices exteral tothe onal volume, such a a dynamometer. Tied, ether forms of work may be present in special situations. For example, ifthe boundaryAdvanced Thermals “UnAL CORSOANATION OF ANY PRIRCUR POM A CONTI YOLEN 1 of the control volume is not rigid, boundary or P dV work may occur. The second ‘and third forms of work discussed above will be lumped together a8 Wag, in the ‘conservation of energy principle, On the basis of the preceding discussion Eq (1-37) may be written as dey dr 0 + Wher + (Pohtitn ~ (Peoatiton = Cinta + eatin — (1-38) ‘where the term Waa, represents shaft work and any other forms of work associated with the control volume. In applying Eq. (1-38), we commonly restrict the types of energy associated with flow of mass across the system boundary to internal, linear kinetic, and gravitational forms. That is, ve onus ee (139) In addition, fh = u + Pe. By collecting common terms in Eq, (1-38), and by ‘making use of the preceding expressions for ¢ and h, the energy balance on a rate basis for a control volume with multiple inlets and outlets is written as aloe en) =e aw 0 tne + Dali Fee) Be All terms on the left of Eq. (1-40) represent interactions which add energy to or remove energy from the control volume. The term on the right is the resultant ‘change of enerey of the control volume due to these interactions. By an analysis ilar to that used above a conservation of mass (or continuity of flow) principle ‘on a rate basis for a control volume takes the form Sin Dine = Mee at) where the subscripts / and ¢ represent inlet and exit states. This is a general ‘expression for the conservation of mass of a control volume. 15-2 Steady State ‘Many engineering systems can be modeled 3s one of steady state. Ina steady-state ‘control-volume properties at a given position do mot change with time. On the basis of the definition of steady state the total energy within the control volume under steady state remains constant with time. This requires that dE cy/dt = 0. As a result, Eq. (1-40) reduces 10 8 Han Salis Mas) Sale eed ceAdvanced Thermodynamis for Engineers 20 aaste RELATIONS ANDTHE FIRST La The mass flow rates stare not equal at each open boundary for control volumes with multiple inlets and outlets. However, the values are related by the continuity of flow equation. In steady state dmicy/dt = 0. Therefore Eq. (1-41) reduces to Sie Dm (1-43) where fr = paV = AV/o. “There are numerous applications of steady-state processes that involve only one inlet (position 1) and one outlet (position 2). In this circumstance rt; = tre = ft and Eq, (1-42) reduces to + Was = alr See) (ie +e] = ites m+ VIM giea~en] aay The above conservation of energy equation for a control volume with one inlet and one outlet ean be written on a unit-mass basis in the form = (in—hy) + Faqations (1-42), (14), and (1-49) are important statements of the conservat of energy principle for « control volume under steady-state conditions, 1.6 TRANSIENT FLOW ANALYSIS The analysis of nonsteady-flow devices serves to strengthen one’s understanding of and one’s ability 10 use the general conservation principles related to mass and energy. The importance of the proper selection of a control volume often becomes apparent in such analyses. Also, there are useful applications of devices which ‘operate under nonsteady flow, For example, some wind tunnels operate on the discharge of a gas which has been stored under high pressure in a large tank. ‘Compressed air stored in a cylinder might be used to drive « gas turbine coupled with a gonerator as an auxiliary electric power source. In steady-state analyses ‘we usually consider the control volume fixed in space, size, and shape. We now ‘wish to relinguish «wo of these contains and to allow the size and shape to vary, if required. However, the control volume will still be considered to be fixed in location ‘Transient flow problems arise when the control volume is notin steady state. Heat, work, and mass transfer rates, as well az properties at an open boundary, may vary with time. AS a result, properties within the control volume vary. ForAdvanced Thermals TRANSIENT LOW ANALYSTS 21 ‘example, the energy within the control volume varies so that dEey/ dr # 0. Hence ‘we must retun to Bq. (1-40) as a starting point. B+ Dele +s) Sire Yee) = So a ‘This equation can be used to develop other useful forms of the transient flow energy equation. ‘Since some of the terms in the above equation vary with time, the equation ‘ust be integrated over a time ¢ to give the total energy change of the control ‘volume during this interval, Asa result, for a control volume which remains fixed in space so that Ecy = Ucy (lars [oar (4S He) nat Shes ‘To cary out these integrations, we need 10 know how the various properties and rates vary with time, ‘The integration ofthe control-volume energy term on the right-hand side may take one of several formats, depending on the type of process under investigation Among the possibilities are BOE hw = (mu) = ~ mus [ Boeear a [ater = [aad = mana mans = Ale and J avey = | denuy = ima + udm) Both these choices are used in the following section. Another useful formulation ‘of Eg, (1-40) is obtained by multiplying the equations by dt. The resulting re- lationship is valid for a differential change of state for a control volume over a time dt. Thus 30 + 6¥ia + (4 +4) am - “Eb he ee dine = dew aan Integration of iq. (1-47) over a time period of interest yields 04 Wee | (ie Fe an [eM ee) ane = ates cs where only one inlet term and one outlet term are shown.Advanced Thermodynamis for Engineers 22 asic RELATIONS ANDTHE RST LAW In the analysis of transient flow systems several models frequently are ap- plicable to real situations. These include the models of the uniform state and of uniform flow. These are defined 2s follows: 1. A uniform state requires thatthe state within the control volume at any instant bbe uniform through the control volume (or over several different rogions of the control volume). However, the state within the control volume may change with time. 2. A condition of uniform flow requires that the state of the mass erossing a control surface be invariant with time. However, the mass flow rate across that particular conirol surface may vary with time. The condition of uniform state implies rapid or instantaneous approach to equi librium at all times for the mass within the control volume. This is met by many transient fluid systems in practice. The condition of uniform flow is frequently met when the low into a transient system is supplied from a very larze reservoir of matter. In a transient flow system a net accumulation or depletion of mass within the control volume may occur. AS a result, the sum of the rates of mass entering nd leaving the control volume is not zero but must equal the time rate of change of the mass within the system, Symbolically this was given earlier by Eq. (I-41), Sos Dine = Me aan iy sou uansiemt flow problems the mass rate of How vanes with time. In this cease the above equation must be integrated over a period 7 10 give the total mass, change of the control volume during this interval. Therefore > ind “Zima = Amey 49) ‘To carry out these integrations, one needs to know how the mass flow rates at various portions of the control surface vary with time. 1-7_ CHARGING AND DISCHARGING RIGID VESSELS This section deals with two common unsteady-state problems. One of these is the ‘charging of «tank with a fluid from a pressurized line. ‘The other i the discharging of a fluid from a pressurized tank into a region of lower pressure. 1-7-1 Charging Processes A common and typical example of an unsteady-state flow problem is the charging. of a rigid vessel by supplying a fluid from some outside high-pressure source. TheAdvanced Thermals CCHAREING AND oISCHARLING RED vEssLs 23 rigid vessel may initially be evacuated, or may contain a finite amount of matter within it before the charging process begins. Generally, the mass enters only at ‘one section of the control surface and no efflux of matter occurs. ‘As a more definite illustration of the problem, consider an evacuated rigid tank connected through a closed valve to a high-pressure line. This situation is shown in Fig. 1-2(a). A control volume has been selected, as indicated by the ashed line in the figure, which includes essentially the volume inside the rigid tank. We shall assume that the volume in the region of the valve and entrance Pipe is negligible. Application of Eq. (1-48) to this situation reveals that 2+ Wt | (t+ +28) an = ave ‘The net work term is zero in value on the basis of the statement of the process. Usually the kinetic and potential energies of any unit mass in the line may be ne~ lected. ‘Thus the conservation of energy equation for the selected control volume reduces 10 [ham = avev [At this point one must make a decision about the quantity Q. I the tank were heavily insulated or if the tank were allowed to fill rapidly, the amount of heat transferred would be quite small even if an appreciable temperature gradient existed between the contents of the tank and the environment. Therefore we shall analyze the process on the basis of negligible heat transfer. The overall internal (o Ofensyster (0) Closed sysem FIGURE 1-2 ‘wo methods of analyzing the charging of a vessel.Advanced Thermodynamis for Engineers 2A aASIC RELATIONS 4D THE FIRST LAW energy change of the control volume can be written as A(mu). Thus the above energy equation becomes {dm = myuy mini (1-50) ‘here i and f represent the initial and final states within the control volume. The integration is carried out from zero mass to the final mass which enters from the line. Frequently the integral of h dm is difficult to evaluate because the enthalpy of the mass crossing the control surface varies with respect to time. However, in cur particular case we can assume that the quantity of fluid bled from the line is small compared to the quantity flowing through the line. Consequently, the properties of the fluid atthe entrance to the valve remain constant, 90 we have a case of uniform flow. If we designate the line conditions by the subseript L, then integration of the above equation leads to lm, = 0) = myuy ~ miu; ‘here the terms on the right refer solely to the control volume. For this particular problem m; is zero (the tank intially was evacuated), and thus my equals m Hence hump = miny or hy =uy This relationship fixes the final state within the control volume. Under the con- ditions specified the enthalpy of the fluid in the hivh-pressure line is numerically equal to the internal energy of the fuid within the control volume if a uniform State exists within at any instant. ‘The above result is completely general in the sense that the nature of the ffuid has never been specified. Although equally applicable to any real sas, the ‘equation above is of special interest when employed for the flow of an ideal gas into the tank. Since h = ¢,T" and u = ccT for an ideal gas (if the values of the two specific heats are assured constant over the required temperature range), then et = coy or Ty = kT where k is the specific-heat rato. This important result shows that Ty is always aveater than T;, for the flow of an ideal gas into a rigid tank under the following ‘major idealizations: 1. Adiabatic, rigid control volume 2. Uniform state within the tank at any instant 3. Negligible kinetic energy of the inflowing gas 4. Uniform inlet flowAdvanced Thermals ‘uaneINe AND DISCHARGING RIED veSsMIS 25) Since & for many gases ranges ftom 1.25 to 1.40, the absolute temperature rise may be as much as 40 percent. For real gases one will ave to rely on tabular data in order to ascertain the final state of the fluid after it reaches a certain pressure ‘within the tank ‘The problem of charging a tank from a steady-flow fine is amenable to an- alysis also on the basis of a closed system. The closed system selected for anal- ysis is shown in Fig, 1-2(6). The conservation of enetey equation in this case is O+W=ae ‘Again, we shall neglect kinetc- and potential-energy terms and assume adiabatic conditions. The energy equation becomes W = AU = myuy ~ mus Unlike the contol-volume approach, however, neither the work ferm nor the tial mass term mm; is zero. The work done is the boundary work related to shing the mass contained within the system, but outside the valve, into the tank. Consequently the energy equation becomes PW Vi) = myuy — mise or =P ~ mer) = myuy ~ mime Finally, combining the second term on the right with the term on the left, we find that (Pre + We and f= uy ‘This result is identical to that obtained by a control-volume analysis. Both were based on comparable idealizations, However, it should be noted that the terms included in the two analyses are quite different. mys 1-7-2 Discharging Processes From a physical viewpoint the discharge of a fluid from a pressurized vessel is similar to the preceding case of the charging of a vessel. However, fom a ‘thermodynamic viewpoint there is litle similarity in the relations which result from applying the conservation of energy principle tothe two processes. We shall again neglect the kinetic and potential energies associated with either the control volume or the mass leaving the vessel through a suitable valve. Thus ¢ = 4. The absence of shaft work again is noted. In the absence of specific information on heat transfer we shall assume that the effect is negligible. If Eq. (1-47) is now applied to the contro! volume shown in Fig. 1-3(a) and the above comments are taken into consideration, we find that (u + Poydm = dUey or dm ~ d(mu) = mdu + udmAdvanced Thermodynamis for Engineers 26 ASIC RELATIONS AND THE FIRST LAW , L @ » {) Schematic dagsam, () Pe process diagram fr flow fen pressurized vessel ‘This problem ic unlike the charging of a vessel from a pressurized line ie that the properties of the fluid crossing the control surface are continually changing. For this reason we have elected to write the conservation equation in its differential form. The above equation can be arranged into the following forms: (h—u)dm = mdu du__ dm It should be noted that the specification of property valves, such as h and 1. for the mass within the control volume requires thatthe fluid be essentiall equilibrium at all times. Hence the process of discharging the gas is quasistatic and one of uniform state. ‘The equation above is completely general. That is, we have not specified ‘the nature of the fluid leaving the pressurized tank. We may introduce two further relationships without losing this generality. First of all, from the definition of the enthalpy function h— w= Pe. Second, the volume of the control volume remains constant with time, Then from the basic definition V = mo we find that dV = mde+ odm = 0. Therefore 1 ‘Substitution of these two basic relations into the conservation of energy equation leads to ‘or upon rearrangementAdvanced Thermals CHARGING AND DISCHARGING RIGID vESsaLS 27 For a closed system of fixed composition the first 7'ds equation [Eq. (1-11)] requires that Tds= du+Pdo aay {or a simple compressible substance, regardless of the nature of the process. Com- parison of these last wo equations forces one to conclude that, for the process, ds =0 (flow from a pressurized tank) ‘Therefore for any Muid which flows from a pressurized vessel under the stated ‘assumptions or idealizations the specific entropy within the control volume remains Constant. The total entropy of the control volume decreases, however, since the amount of mass decreases, The overall process is highly irreversible so that the net entropy change of the control volume plus its environment must be positive. Figure 1-3(b) illustrates the process path for the discharging of a fluid from «4 pressurized tank. The path is for the fluid which remains inside the tank. Note that such a process must fulill the following idealizations: 1. Adiabatic, rigid control volume 2. Bquilibrium within the tank at any instant (uniform state) 3. Negligible kinetic- and potential-energy changes The fact that the process is isentropic is not surprising, since itis adiabatic and uasiotatis aid all intcinal dissipative effets and finite gradients havc been ruled ‘out. That is, the process within the tank is adiabatic and internally reversible. ‘As a specific example, consider the flow of an ideal gas from a pressur- ized tank, The approximate validity of the ideal-gas equation will depend on the pressure range involved. Since the process is isentropic, the isentropic relations presented in Sec. 1-1-4 for ideal gases are valid for relating pressure, tempera- ture, and specific volume. A relationship for the mass remaining in the tank at ‘any instant can also be obtained for an ideal gas. We noted earlier for a constant volume process that In addition, if one assumes constant specific heats, the isentropic relation Tey yieldsAdvanced Thermodynamis for Engineers 28 asic RELATIONS AND THE FIRST LAW Therefore equating do/e in the last two equations leads to 1_ar _ dm tT me Finally, integration of the above equation yields na _ (TI mor If the pressure ratio is known, the comparable equation is mz _ (P2\* mG) AA third equation can be derived for the mass as « function of the specific volume, or density. Bxample 1-1, A tank with a volume of 1.5 ai is filled with air at a pressure of 7 bars and a tempeniture of 250°C. Determine (a) the final temperature, (6) the Percent of the mass left in the tank, and (©) the quantity of mass, in kilograms (kg). ‘that left the tank if the gas is permitied to leave the tank under adiabatic conditions ‘uni the pressure drops to 1.0 bar Solution {(@) Under the conditions ofthe problem itis realistic to assume ideal-gas behavior 1 the mass within the tank changes its state isentropically, then, since & is roughly equal to 1.4, (8) The percent of the mass eft inthe tank can be found from the relation vt fe) -G Troe ot 28 pe ts ef en eso bari ead, Titclompenteds ur we (Temas ily nth ak ven bye eg aon Py _rou.s2407 RE > 0.083155) Hence the mass bled from the tank is 0.751(7.00) = 5.26 ke 249 .00 kg ‘There are many other types of transient flow problems of theoretical, as well 4 of practical interest. The solution of each type depends on the restrictions and ‘idealization placed on the process. In every case it is best to begin with basic or fundamental equations and to proceed logically from that point.Advanced Thermals 'RANSIENT ANALYSIS WITH BOUNDARY WORK 29° 1-8 TRANSIENT ANALYSIS WITH BOUNDARY WORK Consider the situation shown in Fig. I-f. A weighted piston-cylinder assembly initially containing a known quantity of a gas at a known equilibrium state is ‘connected through a valve to a high-pressure line. To simplify the problem, the fluid in the line is the same as that in the piston cylinder. We are interested in ‘determining the temperature and the quantity of mass within the eylinder after the volume has changed by a known amount. Since the upper boundary will move, the control volume shown in Fig. 1-4 changes size and boundary work occurs. Te is necessary to place a restriction on the process if the boundary work is 10 be evaluated. Even though the pressure in the line may be substantially above the pressure within the cylinder (as maintained by the weighted piston), we must assume that the entering gas quickly equilibrates with the gas already present in the control volume, Thus @ uniform and constant pressure P is maintained by the piston on the gas. Then the work done by the gas on the surroundings is simply ~PAV. We shall assume that the process is adiabatic and thatthe entering velocity is negligible. Although the center of mass of the control volume changes in elevation, this potential-energy effect can be neglected. As a result, The basic conservation of energy equation for the control volume «ase, based on Eq. (1-48), is O + Woat + Mooutay * fu + Po)dm = Mev For this specific situation the above equation reduces to Wana + | n= Ate FIGURE 14 ‘A contol volume witha moving eonyAdvanced Thermodynamis for Engineers 30 asc aris AN THE PRT LAW In terms of the properties forthe intial and final states we find that SPU = vy + | helm = yay — mon ‘As a final step, since the flow through the line is steady, we can integrate the ‘quantity dm directly and obtain the equation =P, — Vi) + hymy, = myuy — min, «sty where the line condition is designated by the subscript “Z.” The unknowns in this ‘equation are my, my, and uy. However, the mass quantities are related by my, = my mm mus we actually have one equation with two unknowns, my and 1 The second required relationship in this case is found from « knowledge of the final volume. Note tht Vj = mo. Since Vis given the unknowns in this relationship are mj and o;. Hence another unknown, by. is introduced. However, uy and v7 ae not independent variables, On the basis of the ste principle for a given pressure within the contol volume only 1; oF cy can be varied independendy, but not both, Thus a suitable equation of state which uniquely relates uy and ey fora given P isthe deste tid elation which permits the (wo equations already presented to be satisfied Example 1-2. A piston-cslinder assembly is attached through a valve to @ source of air which is owing in say state through a pipe. Initially, inside the cylinder the volume is 0.01 m’, the temperature of the air inside i 40°C, and the pressure ‘is 1 at. The valve 1s then openea to tne ai-supply line which is maintamed at © boars and 100°C. If the cylinder pressure remains constant, what will be the final = 0.86 KUAkg-K and (b) the gas data ae obtained from the superheat table, 1-23. ‘wo tanks of the same volume are connected by a pipe containing a valve, Initially, the valve is closed, one tank is evacuated, and th ether tak contains 40g of steam {av 15 bars and 280°C. The valve is opencdl and the seam flows into the evacuated ‘aak uatil pressure equilibrium is reached. If the steam temperature atthe end of the proces is 440°C in both tanks, determine 2 the final equilibrium pressure. in bars . the eat transfer, in kilojoules . the entropy change, in KK, of the steam 4. the foal entropy change, in KK 1-24. An insulated tank with volume of 050m contains air at 1.0 bar and 25°C, The tank is connected through a valve to a line which caries air continuously at 7.0; brs and 177°C. Ifthe valve is opened and iris allowed to flow into the tank until the pressure reaches 5.0 bars, determine (a) the amouat of mass which has entered, in kg, and (b) de final temperature of the air inthe tank, im degrees Celsins, (Use constant specific heat data in your soation.) 125. A tank contains R-134a at 14.0 bars and 60°C and has a volume of 0.20 m3, The ‘contents ofthe tank are heated, but a relief valve allows fd to escape so thatthe ‘pressure remains constant. Ifthe final temperature #8 130°C, find by 2 least square fit of data and numerical integration or by graphical integration the quantity of heat flded, in Kilojoules. 41-26, A very lage reservoir contains steam at 20 bars and an unknown temperature Tp Steam is allowed to flow from this reservoir into a small insulate rigid tank with a volume of $.0 m?. The tank initially contains saturated water vapor at 10 bas, The flow of steam from the reservoir continues until the pressure inthe tank builds up to 20 bars. AC this instant the measured temperature in the tank is 320°C. Determine the temperature Ty ofthe reservoir, in degrees Celsvs, 1-27. A very latge reservoir contains alc st 10 bars and an unknosen temperate Tp. Ait is allowed to flow from the reservoir into a small insulated tank with a volume ‘of 0.150 m. The tank iitaly contains air at 2.0 bars and 27°C. The flow fom the reservoir wo the tank continues until the pressure im the tank builds up to 4.0, bars. AC this instant the measured temperature in the tank is 87°C. Determine the temperature Te of the reservoir, in degrees Cel it, an ideal gas with constant specific heats, dows slowly from the atmosphere at Ty and P, into an insulated cylinder ited wih asprin loaded piston. The spring is near that i, the frce-displacement relation i straight ine. Initially, the volume of air in the cylinder is zero. ‘The spring is preloaded so thatthe pressure at the piston face must rise to %y before the piston will move, Whea the eylinder pressure Feacnes rg. tie Volume 18 Vj. Assume constant specitc heats, (a) Show that the temperature of the air in the Cylinder at this point is given by 1.28,Advanced Thermals 129, nat. rromuzne 37 {In addition, determine the value of 1 under the special conditions that (b) Py = and (©) Pp = Pe A piston cylinder assembly maintained ata constant pressure of 1.00 bar (weightless piston) initially consains 0.0010 kmol of air at 27°C. The assembly is connected to an air lie maintained at 7.0 bars and 400 K. Air is allowed to flow from the Fine tothe assembly until the volume is doubled. During this process hest enters the cylinder in the amount of 1000 kVkmol of gas finally in the tank. For ai, let = 20,97 and f= 29.277, both expressed in kUkmol and with Tin kelvin. ‘Use & comtrol-volume energy analysis to derive an equation in the form CANsTy + CANy + Cy ~ 0, whore Cy, Czy and Cy are numerical values and the subscript f stands for the final state in the cylinder. ». Derive another independent equation which shows that NjTy = C4, where Cy is come numerical value ‘6. Determine the wiluos of the mace which has entered the assembly, and the final temperature inthe eylinder, in Kelvin ‘A tank containing, R-134a at 12 bars and SOC has a volume of 0.10 m?. ‘The ‘contents of the tank are heated, but a relief valve allows fluid to escape so thatthe pressure in the tank remains constant. Ifthe final temperature is 120°C, determine by ‘east square fit ofthe data and numerical integration (or by graphical integration) the quantity of heat added, in kilojoules. "The upper tenk in Fig. PI-31 contains 0.060 m? of steam initially at 80 bars and 400°C. The lower tank contains a liquid which isto be forced out by admitting steam from the upper tank. The Fiqud initially completely fils the lower tank, and kilomoles, Steam #0 bars ‘anc | FIGURE P13Advanced Thermodynamis for Engineers 38 asic naLaTiOns ND THE FIRST Lave the steam and liquid are not miscible. The pressure in the lower tak is kept constant at 30 bars by means of a valve between the two tanks. The steam continues to push liquid from the lower tank unil the pressure in the upper tank has fallen to 30 bars. There is negligible heat transfer between the tanks, between the tanks and the surroundings, and between th liquid and the steam. Determine a. the final temperature of the steam inthe upper tank, in degrees Celsius Di. the final temperature of the steam in the lower tank, in degrees Celsius . the volume ofthe liguid displaced, in cubic meters (Suggestion: Leave your analysis in terms of symbols as long as possible, Some analyses require a least square fit and numerical integration.) 1.32. A. pressurized tank contains 0.1 kg of water vapor at 40 bars and 280°C. Mas is allowed to flow from the tank until the pressure eaches 10 bars. However, during the ‘process heat i added to the uid within the tank to keep ita a constant temperature Determine the amount of heat adda, in klojoues, DY a solution which requires approximating the enthalpy of the steam leaving the tank 4 solution wien requires a least square curve fit of ata and numerical imtegra- 1.33. Rework Prob. 130 under the following conditions. The tank of volume V initially ‘contains an ideal gas at Pt and T;. Heat i added until the temperature rises 10 72, the pressure remaining constant. Derive an expression forthe total heat transferred ‘during the process. Q. in terms ofthe independent variables, P. VT), Tx, and the specifiesheat ratio k 134, A 1.0-m tank contains 0.5 m? of R-134a saturated liguid and 0.5 m? of saturated vapor at 9.0 bars. The tank is fted with a pressure relief valve that allows only Saturated vapor to escape and that keeps the pressure inside the tank constant. [Determine the heat trancter ein, in Filojoules, to evaporate one-half the mass of Liguid R-134a that was eriginally present. 1.35, Saturated steam in the amount of 0.10 kg initially is maintained a 1.0 bar within a piston-clinder assembly. The pressure within the cylinder is maintained by a spring ‘nthe other face ofthe piston, A steam line containing saturated steam at 9.0 bars ’s connected tothe assembly through a valve. The valve is opened until the pressure in the cylinder reaches 5.0 bars. Dusing the petiod of time Ut the valve is opened hea transfer to the cylinder contents is 32.0 KJ and 0.20 kg of steam flows into the cylinder. The work done on the spring is 40.0 KJ. Determine the final quality (if Saturated) or the final temperature in degrees Celsius (if superheated) ofthe steam ‘within the cylinder REFERENCES 1, Poincaré, H. Thermadsmonigue, Georges Cane, Pais, 1892 2. Caraedory, C., Math, Ann. (Belin), 67388386, 1909. [Eaglsh wanslation, J. Ken, el, The Second Law of Thermodynamics, Put 1, Dowden, Hutchinson, and Ross, Suoudsburg, PA, 1976. 3. Rejn, A., Adtanced Engineering Thermadpnamics, Chap. 1, Sohn Wiley & Soas, New York, 198 44. Clava, F G..and J. L. Smith. Je. Eneinering Thermadsmemics. Pan. Boston. MA. 1981 5. Zemansky, Me, Hear and Thermeavames, 30 0, MeGraw Hl, Tc, New York, 1968 6. Hatsopouios,G. N., and J. H. Keenan, Principles of General Thermodwamics, John Wiley & Sons, New York, 1965Advanced Thermals CHAPTER 2 THE SECOND LAW OF THERMODYNAMICS In an introductory course in thermodynamics attention is focused on the sec~ ‘ond law and related theorems and corollaries. The concepts of reversibility (and ineversibility), entropy, and entropy production are important in the analysis of energy processes and sYstems, Certain types of reversible eyclic eyuipment, ealled Carnot devices, are found to be useful in the study of simplified heat engines, refrigerators, and heat pumps. These and other related topics will be reviewed and extended in this chapter. 2:1 THE SECOND LAW FOR CLOSED SYSTEMS ‘The early development of the steam engine occurred in the latter half of the eighteenth century, The conversion efficiency of heat to work of these early devices ‘was usually less than 5 percent. An important first step in the theoretical analysis of heat engines was a memoir by Sadi Carnot, a French engineer, in 1824 [1]. This work was an early step historically in the development of the second law. Although developed in the era of the calorie theory, it correctly presented some ‘important principles which still bear his name (and will be reviewed shortly). "The two statements of the second law most frequently cited in introductory textbooks are those due to Clausius and to Kelvin and Planck. Both originated in the middle of the nineteenth century. Both are based on observations of specific imeversible processes. 39Advanced Thermodynamis for Engineers 40 THe secon LAW OF THERMODYNAMICS Both state that the reverse of these observed processes cannot occur naturally, 11 is observed that heat always flows spontaneously (of its own accord) from a region of higher temperature to one of lower temperature. In 1850 Clausius postulated that the reverse process is impossible. ‘That is: Heat cannot pass spontancously (unaided) from region of lower temperature toa region of higher temperature ‘The inclusion of the word “spontancously” inthe Clausius statement of the second. {aw is eritica. eat will pass from a lower toa higher temperature if an appropriate deviee (a refrigerator or heat pump) is used as an aid. But the absence of such a device precludes the passage of heat spontaneously. The Kelvin-Planck statement focuses on the heat-o-work conversion pro- ‘cess. The first law places no restriction on the conversion of heat ito work oF Work into heat. The latter process is observable, for example, through a frictional process. However, it was also observed that a heat engine (closed, cyclic heat- {o-work converter) would not operate if it received heat from a single source. Hence a major restriction existed in the design and operation of heat engines, This was first recognized formally in 1851 by William Thomson (Lond Kelvin) {2}, who stressed the impossibility of producing work by some device by means of cooling matter below the temperature of the surroundings. Another version of| this approach, using the concepts of a cyclic device and a heat eservoie, was Presented in 1997 by Planck [3]. In honor of both sciemsts the Kelvin-Planck statement of the second law may be paraphrased in the following manner: It's impossible to construct a heat engine which produces no other effects than the extraction of hea from a single source and the production of an equivalent amount of wok. ‘A device which violstes the above statement is known as a perpetual-motion ‘machine of the second kind (PMM2). It produces work solely by the cooling of ‘a body. Hence we cannot directly use the vast quantities of energy in the oceans and the atmosphere on earth to produce work without some additional changes taking place in the interacting systems. ‘The preceding second-law statements rely heavily on observations made with respect to cyclic devices such as refrigerators and heat engines. Since the second. Jaw has general applicability to a wide range of phenomena, it should be possible to provide other formulations which avoid reference ta specific applications, One Of these is due 10 Hatsopoulos and Keenan [4], who define a stable equilibrium state of a system such that a finite change of state cannot occur without a cor- responding finite change occurring in the state of the environment, Making use of this definition, Hatsopoulous and Keenan proposed the following second-law statement in 1965: AA system having specified allowed states and an upper bound in volume can reach from any given state a stable state and leave no net effect on the environmentAdvanced Thermals ‘We SUCOND Law FoR cLOstD SYSTEMS 41 ‘This statement, which is not deducible from the definition of a stable state, simply predicts the existence in nature of stable equilibrium states. In 1909 Carathéodory 5) presented a highly mathematical approach to the second law. As reworded by ‘Zemansky (61 In the neighborhood (however close) of any equilibrium state of a system of any ‘numer of thermodynamic coonlinates, there exist states that cannot be reached (are inaccessible) by reversible adiabatic processes. He showed how to derive from this statement all the consequences usually 35s0~ ciated with the methods of Kelvin-Planck and In tum, Landsberg (7] Inas shown that Carathéodory’s principle can be deduced from Kelvin's principle. ‘The work of Landsberg cited above is an example of the equivalency of various second:-law statements. All four ofthe second-Iaw statements discussed in this section are entirely equivalent. This means that all the theorems and corollaries ‘derivable from one statement are inherent inthe other statements. The equivalency of two statements is determined through the principles of mathematical logic. The equivalency of two statements, X and Y, is written symbolically as xey en Equivalency occurs if, and only if, the negation of one statement implies the negation of the other statement, and viee versa. The symbol used for “implies” is. Hence the validity of Eq. (2-1) requires symbolically that -X>-¥ and -Y+-¥ (22) ‘This technique may hee sed to verify the complete 64 ‘native statements of the second law presented above. ‘The early development of topics such as mechanics, electromagnetic theory, and thermodynamics was based in each ease on inductive analysis of macroscopic experimental observations. In thermodynamics the observations of certain pro- cesses lead to the concept of state functions such as energy and entropy. Later in the history of each of these fields @ postulational approach was shown to be more concise and internally consistent. An important postulational approach 10 ‘thermodynamics is found in the text by Callen [8]. In this approach the concepts of state functions, energy, and entropy are presented as fundamental concepis. The postulates presented by Callen in his text are as follows: valence of the four alter- Postulate I, “There exist particular states (called equilibrium states) of sim- ple systems that, macroscopically, are characterized completely by the intemal energy U, the volume V, and the mole numbers Ni. Nz... N, of the chemical components.” Postulate IL,“There exists a function (called the entropy $) of the extensive ‘parameters of any composite system, defined for all equilibrium states and having ‘he following property. Ihe Values assumed by the extensive parameter in die absence of an internal constraint are those that maximize the entropy over the ‘manifold of constrained equilibrium states.”Advanced Thermodynamis for Engineers 42 se secon Law oF rHERMODENAMICS Postulate IH. “The entropy of a composite system is additive aver the con- stituent subsystems. The entropy is continuous and differentiable and is a mono- (onically increasing function of the energy.” Postulate TV. “The entropy of any system vanishes in the state for which (GU/aS)y7 = 0, that is, atthe zero of temperature.” Note that the internal energy and entropy play a dominant role in these postulates, Contained within these postulates are the zeroth, first, second, and third laws, ‘and the state postulate found in conventional thermodynamic textbooks based on inductive logic. 2.2 REVERSIRILITY ‘Two of the major goals of second-law analysis are: (1) determining the “ideal” or “theoretically best” performance of energy devices and (2) evaluating quan- ‘atively the Tactors that diminish performance in actual practice. Such analysis requires an understanding ofthe concept of reversibility and the reversible process. In general, a reversible process is defined as follows: A process commencing from an initial equilibrium state i called reversible (or totally reversible) if at any time during the process both the system and the environment with which it interacts can be returned to their initial states. ‘The concent of reversihility hy its definition mains restanabifity Rint the rex quirement of restorability is quite strong. applying to both the system and the surroundings with which it interacts. Normally interest is centered during a given process solely on the system. However, a reversible process requires something of the environment. As a consequence of the definition of a reversible process, it is the nature of a reversible process that all heat and work interactions which occur during the original (forward) provess are equal in magnitude but oppo- site in direction during the reversed process. Thus no net history is left in the surroundings when the system regains its initial state, The reversible process is an idealization. It is 4 concept which can be ap- proximated very closely at times by actual devices but is never matched, There are ‘wo fundamental reasons that actual processes are never truly reversible. First, we require the absence of solid friction at the bearing surfaces of pistons, flywheels, and other mechanical devices. A capacitive-inductive circuit should not contain 4 resistive element, and a spring must be made of an ideal elastic material. In many actual cases the effects of friction, electric resistance, and inelasticity can be substantially reduced, but their complete elimination is not possible. These physical phenomena are called dissipative effects, because in all cases a portion fof the energy in the aystem is converted ut dissipated tw a leas uaeful fous. Only in the absence of dissipative effects can a process within an isolated system be considered (totally) reversible.Advanced Thermals revensiwury 43 A second criterion must be met if a process involving a system and its local environment is to be reversible. The requirement that a process be quasistati ‘order to be reversible is a general one. Thus only infinitesimal unbalanced forces are present during a reversible process. For example, heat transfer is not reversible if its occurrence is due to a finite temperature difference AT’ between the system and its surroundings. The transfer of heat is made reversible if the temperature difference between the (wo interacting systems is made infinitesimally small, that is, of magnitude dP. ‘An irreversible process is such that either the system or its surroundings ‘cannot be returned to their initial states. Any system which is returned 10 its initial stare after experiencing an irreversible process will leave a history in the surroundings due to the irreversibilties. leversibilites arise from the two sources ‘outlined abow 1, Presence of inherent dissipative effects 2. Presence of u nomyuasistaic process ‘The presence of either class of effects is sufficient to make a process irreversible. Since all actual processes include such effects, the reversible process is a limiting process toward which all actual processes may approach in performance but may never succeed in realization. Nevertheless, a reversible process is an appropriate starting place on which to base thermodynamic calculations. ‘The absence of inherent dissipative effects and nonequilibrium effects in a system and its environment leads to the concept of a forally reversible process. Frequently it is advantageous to consider processes for which irreversibilities are absent within the system but are not necessarily absent trom the surroundings. Such processes are called internally reversible. Only quasistatic work interactions ‘may occur during internally reversible processes. Work effects associated with paddle wheels or electric resistors within the system are not permitted, since these effects by nature are irreversible. Finally, an externally reversible process is one for which ireversibilities may be present within the boundaries of the system of interest, but the surroundings which interact with the system must undergo only reversible changes. Tn the development of second-law concepts, itis useful to imagine systems ‘which can supply or receive energy in the form of heat or work in an internally reversible manner. These two idealized systems are known as heat and work reservoirs. A heat reservoir is defined as a closed system with the following characteristics: 1. The only interactions of interest across its boundaries are heat interactions. 2. Changes within the reservoir are internally reversible. 3. Is temperature remains uniform and constant during a process. ‘The only significant property of a heat reservoir is its femperarure, which rust remain constant. Internal reversibility implies that there are no dissipative effectsAdvanced Thermodynamis for Engineers 44 re secon Law oF taeRNODYNAMICS Within the reservoir during a change in its state. A heat reservoir simply acts as a ‘heat source or heat sink during a process, depending on whether the direction of the heat transfer is from or to the reservoir Its an idealization which in practice is closely approximated, for example, by portions of the environment. Because the ‘name is a misnomer, this type of reservoir frequently is called a thermal energy reservoir, or simply & thermal reservoir. Heat transfer to of from a thermal energy reservoir results in an increase or decrease ia the internal energy of the reservoir. Another useful concept in thermodynamics is that of a work reservoir. Anal- ‘ogous to a heat reservoir, a work reservoir acts solely as a source or sink for the exchange of work with another system. Changes of state of a work reservoir occur in an internally reversible manner. Any idealized mechanical, electric, magnetic, or elastic system could operste as a work reservoir. Examples include frictionless plley-weight systems aud wotaing Aywheels, and elastic speings, among others, 2.3. CYCLES WITH TWO HEAT RESERVOIRS ‘The Kelvin-Planck statement of the second law precludes a heat engine producing work while receiving heat from a single thermal reservoir. That is, the net work for the cycle cannot be negative (output). However, there is no restriction on the possibility of net work input or zero work for the closed-system cycle, Thus an ‘analytical expression for the Kelvin-Planck statement of the second law is YS Wenea = 0 (single thermal reservoir) (2-49) x $ 8¥Vua = 0 (single thermal servo) aay (Recall that work input is defined as positive im this text.) In addition, for a cyclie process of a closed system SW = => Q. As result, another important analytical form of the Kelvin-Planck statement is Sumas = 0 (single thermal reservoir) 4a) oat or $ 6Q=0 (single thermal reservoir) (4b) ‘Thus a sign restriction exists on W and Q for any closed system which under= _g0e8 an integral number of eycles while in communication with a single thermal reservoir, In terms of the concept of reversibility the equality sign in the above ‘equations applies when the process is totally reversible. The inequality sign ap- plies when irreversibilitics are present during the cycle. The proof appears in a umber of introductory texts of thermodynamics, ‘The next logical step is ta determine whether 2 heat engine ix possible which operates solely between wo different thermal reservoirs and whether there are sign restrictions on the heat terms. A schematic of such a heat engine, labeled A,Advanced Thermals CevCLES WITH TWO MEAT RuseaVouRS a5 "Merma reseroe aT ‘Tremal esenoie st 7 FIGURE 241 Schematic of heat engin operating between two diferent thermal reservoirs ‘which operates between temperatures 7} and 3 is shown in Fig. 2-1. The arrows for Qa and Q2 are arbitrarily shown in a positive direction relative to the heat ‘engine, However, in general, the heat terms might be negative. The limitations on the cyclic engine A are determined by first- and second:-law considerations, The first law requires. that On tQn+ Wa =0 ‘where the work output W, is negative value for the heat engine. With the sign con W, fixed, there are three possibilities or options for the signs onthe heat terms ‘One option can be ruled out immediately. Both Qy and Qaz cannot be negative, ‘based on the frst-law statement above. However, the first law permits two other 1, Both Qa and Qaz are postive in value 2. Qay ainl a2 ate uf upprnite sigur such that te product QqiQaz <0 and the absolute sum [Oar + Qual > 0. ‘The possible validity of these two remaining options depends on the application of the second law in the form of the Kelvin-Planck statement. Figure 2-2 shows heat engine A operating according to option 1, where both Qx and Qug are taken into the heat engine from thermal reservoirs 7; and 7, respectively. Also, operating in conjunction with reservoir T is eyclic device B. ‘Since only one reservoir is in contact with B, the Kelvin-Planck statement requires that Qp <0, Now A and B cach undergoes an integral number of cycles so that Qa2 = —Qp2- That is, the heat rejected by system B to thermal reservoir T2 ‘equals the heat supplied by thermal reservoir T; to beat engine A. Thus reservoir Th also undergoes a cycle. As a result, the composite system of A, B, and To, shown by the dashed line in Fig. 2-2, undergoes a cycle and produces work while ‘exchanging heat solely with a single reservoir at 7). This violates the Kelvin- Planck statement, The only assumption made in this proof is that both Qa, and ‘Qo are inputs to the engine. Therefore this assumption cannot be correct, and option I is invalid. In conclusion, the heat engine shown in Fig. 2-2 cannot operate with both heat inputs or both heat outputs. Only option 2 is a viable alternative such thatAdvanced Thermodynamis for Engineers 46 1s secon Law oF THERMODYNAMICS Reservoir at 7 lou > Composite systems Wy ‘Tremal reser ot, ‘Schematic for resolution ofthe valiity of option I for a two-hermal- reservoir bet engine. Quy and Qua are of opposite signs and their net value is positive, (This alternative does not violate the second law, as noted below.) Hence all heat engines operating between two thermal reservoirs of different temperature must have heat supplied from one reservoir and rejected to another reservoir. However, one point remains unresolved. We know that T) 7 Tp, Dut the sign on (7 ~ Tz) 1s not known, The question is, does the larger of T; and 73 match up with the heat-supply reservoir or the heatrejection reservoir? Some other information on the ratio Q2/Qy must be ascertained before the preceding question js resolved. Toward this end we shall define a Carnot-type ‘heat engine as one which operates ina totally reversible manner while exchanging heat solely with two different thermal reservoirs. The nature of the actual device is unimportant. The definition does require that the engine itself be internally reversible and thatthe two heat transfers Q and Q between the thermal reservoirs and the engine occur across a differential temperature d7°. Now, consider Fig. 2-3, which shows two heat engines, B and C, operating between the same thermal seservoirs with temperatures 7; and 72, where T2 + Ty. Engine B operates under any arbitrary cycle, whereas engine C operates under a reversible Carnottype cycle. Since engine C is reversible, it may operate as a heat pump (or refrigerator), as well as a heat engine. The values ofall interactions will be of equal magnitude but opposite in sign when reversed. For the purpose ofthe following proof eyelic device C is shown operating in the reverse direction from that of engine B. We also shall arbitrarily set Qa1 > 0 and Qp2 <0 with respect to engine B. Finally, to take advantage of the analytical form of the Kelvin-Planck statement as given by Fa. (2-4b),Advanced Thermals Ccreuns wera Two near msemome 47 Compose system ‘emalesrsu at Fy FIGURE 23, Schematic ofan athitrary heat engine and a reversed Cemottype device C operating between the same two thera reservoir froz0 om) the size and integral number of cycles of each engine can be adjusted so that (Qn + Qcr) = 0. Tht in, the lat rejected by engine C to reservoir T; equale the heat supplied to engine B from reservoir T;. As 2 result, reservoir 7), as well as engine B and reversed Camot engine C, operate in a eyclic manner. A composite system made up of these three subsystems, shown by the dashed line in Fig. 2-3, thus also executes a cycle while exchanging heat with a single reservoir Ts. For the composite system the Kelvin-Planck analytical statement above requires that Ont Qcrs0 Recall that Op; = —Qc, where both sides of this equation are positive. Hence the above equation can be written as Qer _ Deo -22<0 Qn Ger or, after rearranging and multiplying both sides by minus 1, we obtain On _ -c2 = Qn ~ cr srte both sides are still positive in value Beene Qgs < Oand Qs > 0. Because cycle C is tually reversible, the value of ~Qc2/@eci remains the same whether 2-5)Advanced Thermodynamis for Engineers 48 Te SeconD LAW OF THtRMOEYSAMS cycle C operates as a heat engine or a heat pump. In addition, engine B is any (unspecified) heat engine. Hence Eq. (2-5) can be written more generally for any heat engine as, = (=2 - (Be) 28 where the inequality apis to any ieversibe eat engine. Thus. (2-6) states that the absolute value ofthe mio of eat rejected a 7s to beat supplied at for any actual ineversile) heat engine is aways equal to or greater than the value for a totally reversible (Camotsype) heat engine in contact with the same t¥o thermal reservoirs. (A more detailed analysis can be found in Bejen (9) "The themnal effceney ny of any het engine is defined as naw Maal Qr=lOal |, _ 102 Qn a lor (On the hasis of Eq. (2-6) and the above relation we find that Taser = Name an Not unexpectedly, we have shown that the presence of ireversibilities during the ‘operation ofa two-reservoir heat engine reduces its thermal efficiency in compari- son to a totally reversible heat engine operating between the same reservoirs. AS @ consequence, a second important question arses from Eqs. (2-6) and (2-7): What is the limiting (minimum) value of (—Q2/Qy) or the limiting (maximum) value Of ‘laser a8 an actual engine approaches the performance of a totally reversible Ihcat cogine? The answers ty dre yucstous posed in dhis seedon are found tthe corollaries developed below: 2-3-1 Carnot’s Principle ‘The inequality expressed by Eq. (2-7) is the first of three corollaries tothe second, law known collectively as Carnor’s principle. The three corollaries arc: 1. The thermal efficiency of any irreversible heat engine is always less than that of a tally reversible heat engine operating between the same (Wo heat reservoirs. 2, The thermal efficiencies of all totally reversible heat engines operating between the same two heat reservoirs are equal. 3. An absolute temperature scale may be defined which is independent of the nature of the measuring substance, ‘Statement 1 follows directly from Eq. (2-7). The proof of statement 2is as follows. Reconsider Fig. 2-3. only both heat engines B and C are totaly reversible. If the thermal efficiency of either one is acsumed greater than the other, 4 violation of the Kelvin-Planck statement can be established. Thus the assumption is incorrect and statement 2 holds,Advanced Thermals creas meat rwo mar xesemvons 49 2-3-2 The Thermodynamic Temperature Scale On the basis of statement 2 of Camot’s principle the thermal efficiency of to- tally reversible heat engines is independent of the construction, cycle design, and working fluid of the engine. As a result, the limiting values of (~Q2/Q1) and ‘ar can only be a function of T; and T>. They are the only variables left in the design of a totally reversible engine. In the process of secking the appropriate temperature function another Fundamental question arises: What isthe nature of the thermometer to be used for measuring T; and 73? Its well known that ther= Imometers which rly on different thermometric substances frequently are not in 00d agreement, even over reasonably soll temperature ranges. Mathematically the dependence of (~Qz/Q1) om 7; and 72 can be expressed by o: S(Ta,T) 28) Qa where f(T>. T;) is some as vet unknown function and both Q values are considered positive in this discussion, To ascertain the nature of the function, consider the three Camot-type heat engines X, Y, and Z shown in Fig. 2-4. They operate between pairs of heat reservoirs (Ti, 13), (Ti, Ts), and (To, Ts). Application of Eq. (2-8) to the three heat engines in Fig. 2-4 yields Qs 2 5g $n) Gea St) = fuT Since (Q2/Q1) = (Qs/Q1)/(Qs/Q2), then Lu) SO) = Tea ‘The leftchand side of the above equation does not depend on 73, and Ty, Ta» and T; are independent variables. The above equation and these restrictions are satisfied only when the function is written 3s = Hh) Su T) Fe where ¢ is another function. Substitution of this required format into Eq. (2-8) leads to the general relationship, Os _ a) Q on) This isa far a8 therodymamic theory goes. At this point te choice of the mathematical for of €7) i completely ebay. Ary monotonic Furton an Te uned wo define a hermadymane temperature seal which sidependent of the Payal chennoneti) prepares of my subaance, The Kevin scate mes Byzelecung tT) =P. a Carnotype heat engine operass between and T 29)Advanced Thermodynamis for Engineers 30TH stcovD Law oF THsRMODYNAMNCs ‘Thermal reservoir at 7, FIGURE 24 ‘Thre Camottype heat engines operating between slaced pais of te thermal eserves fon the Kelvin scale, then (recognizing that Q and Qin practice are of opposite signs) (2-10) Values on this thermodynamic temperature scale are established by operating Camot-type heat engine between sny reservoir at T and a reference reservoir at Tre. AN intemational committee has set the reference temperature at 273.16 (exactly) on the Kelvin scale for the triple state of water (491,69 on the Rankine seale). The reason for selecting this value is historical in nature, Thus, in general, T (kelvins) eu Where Q and Qry are the quantities of heat exchanged by a reversible heat en- sine between kelvin temperatures 7 and 273.16 for a reservoir atthe triple state ofAdvanced Thermals evcLEs wr TWO MAF seo SL water. A Carnot-type heat engine has another important function besides establish- ing an absolute temperature scale. The device itself can be used to transfer heat reversibly when a finite temperature difference exists between two systems, and Eq, (2-10) is valid for that reversible exchange. The only other way to transfer heat reversibly is to maintain a diferensial temperature difference dT between the two systems. “The major advantage of the thermodynamic temperature scale is its univer- salty. The nature of the working uid is nota factor. Equation (2-10) also provides answers to the two questions posed earlier. Fist, since we choose Qy > 0 and 2 <0 in this development (wcll Fig. 2-3). and W <0, then Q2 f #? ) (reversible process) AA combination of this equation with Eq, (2-18) leads to the generalization that ase [°%0 ey) ‘where the equality and inequality signs apply to internally reversible and. irre- versible processes, respectively. As a consequence, the entropy transfer never exceeds, algebraically, the entropy change. Equation (2-19) leads directly to one form of the increase in entropy prin- ciple. In the absence of heat transfer any closed system must fulfill the condition that AS ya = 0 (closed system) 220) The entropy function always increases due to internal irreversibilities during an adiabatic closed process. In the limiting case of an internally reversible adiabatic process the entropy will remain constant. For an isolated system 8 = 0 by definition. Therefore Sn > 0 221) ‘This second form of the increase in entropy principle is extremely general in its application, because an isolated system analysis includes changes to all subsystems participating in a process. 25 CLOSED-SYSTEM ENTROPY GENERATION In the preceding section the fundamental relaionship dS = 8Q/T was developed for any closed system. This equation le prncece, ant the inequality hold When intemal ireversibilities are present. This inequality can be transformed into an equality by the introduction of the concept of entropy generation.Advanced Thermals uosep svsreM exTmory GexeeaiON 5S 2-5-1 Entropy Generation Due to the inequality in the relationship dS = 80/7, itis apparent that 8Q/T jis not an adequate measure of dS for an internally irreversible process; in fac its contribution is always too small. But the only difference between internally reversible and irreversible processes isthe physical presence of the irreversibilities in the latter case. This implies that internal irreversibilites themselves contribute to the change in S. This contribution, noted by o on an extensive basis and called the entropy production or entropy generation, is always positive. Thus is defined as onm-s-[ Bao (2.22) cor for any closed system or control mass (CM) of uniform temperature Hence the inequality in Bq. (2-19) can be made an equality if a term is added 1 account for the presence of internal ireversibilities. The symbol dm (or o/m) ‘will be used for intensive values of the entropy production. This equation retains the concept that heat transfer always contributes to the entropy change of a closed system, whether the process is reversible or irreversible. This contribution can be positive, negative, or zero, depending on the direction of the actual heat transfer. For a system of uniform temperature Eq, (2-23) on an intensive basis becomes ts = 82 5804 ny toed we) ee is in cts tlre mal eo epi 4) inp (229) al (2.2) oc because enopy practi hat seve: fcc ofp put fe promo Beep rosuea eyed Su te gin of lead esesslce pea aig to pecs, Le Treas at aes yo eel pat ea bo: siya tna Ste pena ont, hen mee paleo ater es acu = 32°24 + 50 225) where 7; isthe temperature atthe point where 8Q, enters. On a unitsmass basis, dsc = SE + 60 2-26) ‘where the summation in both equations is over n different locations on the bound ary, Equations (2-23) and (2-25) also may be expressed on a rate basis. For example, Eq. (2-25) becomesAdvanced Thermodynamis for Engineers ‘50 ue spconD LAW OF THERMODYNAMICS dew = 2 where & = 8¢/dr, the time rate of entropy production due to iereversibilities within the system, The first term om the right-hand side of Eqs. (2-23) through (2-27) is called the entropy transfer or entropy flux term, a8 noted in Sec. 2-8, As a result, these ‘equations may be written as Enuropy change = entropy transfer + entropy production (0-28) Ge) "The term in the parentheses below Kg. (2-28) indicate the possible valuee of the avantities in the equation In summary, Eqs. (2-23) through (2-27) indicate that the change in entropy of any closed system is due to only two separate physical effects 1. One effect is the transfer of heat to or from the system, a8 measured by 8Q.ux/T- This contribution to d§ is called the entropy flux or entropy transfer term, Since the actual heat transfer can be positive, negative, or zero, the entropy transfer term can take on any value, 2. The second effect is the presence of irreversbilities within the system. This contribution is called the entropy production o entropy generation term. This contribution to dS is either equal to or greater than zero. As a consequence, the only way to decrease the entropy of any closed system is to transfer heat from it. However, in this ease the heat-transfer contribution must bbe more negative than the positive contribution of any internal isreversbilties Finally, when Eq. (2-25) is applied to an isolated system, we find that Sint = AS.yy + dS nary * BOue = 0 229) As expected, AS of an isolated system is due solely to the various entropy gen- ‘eration terms within the system, Example 2-1. Oxygen intially at 200 K ane 100 kPa is contained ina rigid tank. ‘Two altemative processes are to be considered to increase its temperature 10 500 K. ‘The gas receives energy (1) adiabatically by means of a paddle wie! driven by ‘an extemal source and (2) by means of an extemal heat reservoir at 600 K. In the second case the temperature at the boundary is taken as the gas temperature throughout the process. Find (a) te entropy production within the system in both ‘cases and (b) the total entropy production in both eases, in kI/kmol K. (c) Then ‘compare the results,Advanced Thermals caammasrstea eximurs Genweanion 57. Solution. ‘The speci entropy generation for a closed system is given by Eq. (2-26), namely tag - Sh mT, (6) () For the paddle-whee! process there is no heat exchanged. Therefore the term ¥ ai/T, = 0. The specific entropy generation, then, is equal othe specilicentopy ‘hange, sp ~ sy. Using data from the ideal-gas oxygen tebe, we find that ry a m= As = §- sf Rin 2 b of —enE rnso9 25218-43042 = 1.181 K ‘where P3/P = T/T; from the ideal-gas equation at constant volume. (2) When the temperature is increased by means of heat addition, there are no appar~ cl sunues wf iucversibilty within the oxygen. Hence om for tic proce i zero. @ (1) If we assume that the work used to drive the paddle whee! came from a work reservoir, then extemal to the tank is zero. Thus the toal entropy production also ‘equals 11.13 kJ/kmol -K. (2) For the heat-adtion process the system boundary is drawn around both the tank tnd the heat reservoir. Thus there i no hea transfer across his boundary and the total ‘entropy production equals the total entropy change ofthe overall system. That Smt = Dteryyn + Mea = (62— SDonyen + HE rt ~ Monger +s Gr seven + “The value ofa isthe negative ofthe heat transfer to the oxygen. This ater quantity js Tound fom an energy balance. Since w = 0 forthe consant-volume proces, = Qu ~ ve = ug~ my = 10,614 6242 = 4372 hnol where the 1 data come from the oxygen ideal-gas table. Hence for a reservar temperature of 600 K Because «rn forthe oxygen in this case is zero, the value of mc is also rg, that due to iereversible hat transfer. {) The values of the total entropy production are quite different, 11.13 versus 3.84 |e/kmol- K. Thus the paddle-whes] procedure i far more ieversible than the beat= Addition process to achieve the same change of state forthe oxygen. There are two factors which could alter this comparison. First, any ireversbiiy in the work mechanism extemal tthe tk would make the use of the paddle whes! even more unfavorable, Second, an increase i the reservoir temperature Tp would diminish the Gifference berwoen the cg Values forthe two processes. For example, a Tp value fof 1000 K would increase oye for the heat-‘ransfer process 10 6.76 K2/xo -K. ‘Thus Tr should be kept as low as possible, consistent with any heat-transfer rate requirement,Advanced Thermodynamis for Engineers ‘58TH Seconp Law OF tueRMODYHAMS 2-5-2. Comparison of Reversible and Irreversible Work Interactions The presence of ieversibilities within a system degrades performance. This is especially important in work-producing and work-absorbing devices. For any in- temally reversible (rev) process of a closed system the T ds equation from Chap. 1 cam be written on an extensive basis as Tas = 8Wer 230) where 6W would be represented by ~P dV for a simple compressible substance Also, for any process involving a closed system the conservation of energy prin- ciple requires that 8Q sci + BWacr = dU 231) ‘The subscript “act” signifies that the 6Q and 8W terms are actual values and apply to either internally itreversible or reversible changes. When Eqs, (2-30) and (2-31) ave applied tv « process with specified end states, dU! tn both equations represents te same quauity, since U is a propeny. If we use Eq. (2-31) 10 eliminate dor from Ei. (2-30), then TAS = 5Qer ~ BWay + 5Wae ‘oF upon rearrangement AScaca = POE + £5 Wa~ Wes) 2-32) However, for any closed system Eq, (223) requires that Sch = 2B = 80 223) A comparison of the last two equations shows that the entropy production 8" of a closed system is related to work interactions by (Bie. — 6Wre) T ‘Thus one of the manifestations of entropy generation is that the reversible and actual work for a process between given states are not equal. In fact, since ois, always equal to or greater than zero (soe Eq. (2-28)]. then Was = Wee (234) ‘This important relation is valid, regardless of the direction of change of the closed system. Hence, laking into account our sign convention for work interactions, we may write bo 20 (2.33) Warsct = Winsey amd — Wout < Wouter (235) ‘Noting that the inequality sign on Eq. (2-34) denotes the presence of irreversibil- ities, we have shown that ireversbilities within a closed system reduce the work ‘output and increase the work input for a specified change of state of a substance.Advanced Thermals Lose SYSTEM ENTROPY GENERATION 59° 2-5-3 Entropy Generation and the Heat-Transfer Process Heat-transfer processes are generally not reversible due to the presence of a finite ‘temperature difference. Hence entropy production is associated with a heat-transfer process. The entropy production is associated withthe space where the temperature gradient exists. Consider the region shown by the dashed line in Fig. 2-6 between systems A and B. To simplify the analysis, we shall assume that the source and sink for heat transfer are heat reservoirs. That is, the heat source and heat sink have constant temperatures 7 and Ty, respectively, and are internally reversible. Ifthe heat transfer takes place at boundaries of the system where the temperature does not change during the heat exchange, Bq. (2-25) may be integrated to the form (2:36) and on a unit-macs basis dsr = E+ 06 ean For the passage of heat from body A to body B the properties of the dashed region in Fig, 2-6 remain fixed during the hea-tranfer process. Hence the entropy change AScy for the region is ze in Eq, (2-36). However, thee are entropy transfers Q/Ts entering and Q/Tp leaving the egio.. Applied specifically 10 the deed in ren of Fie 26 Ea. 2-3 shows te evropy edn ai given 7 oe 2. =o, = TT) 238) where 0g is a special symbol for entropy production due to heat transfer between 4 finite temperature difference, Q is taken as positive in value, and T, > Tp. Equation (2-38) applies to the situation where T and Ty are constant. In some cases either system A or B, or both, may be relatively small. As a result, Systema tT, System Bat Ty FIGURE 2.6 aston for he evaluation of entopy generation during ineveribe heat easterAdvanced Thermodynamis for Engineers (60 Te soconn LAW oF miERMODYNAMICS the temperature of such systems might change significantly due to heat transfer For this more general situation we shall consider an isolated system comprised of systems A and Band the region of space between them (recall Fig. 2-6). Because the term S: Q,/T; is zero for the isolated system, Eq. (2-25) for a finite process reduces t0 01) = ASia. oF for the thee regions 4+ 04 + 09 = AS, + AS, + ASQ Bui Ao for the heat-transfer region is zero by concept. In addition, and B are taken to be internally reversible (variable temperature heat source oe sink only). As a result, 4 = op ~ 0, Thus the preceding equation reduces to 0 ~ ASa> MS 2-39) “Tuy Is the genera solution for a heat-ransfer process between two internally reversible systems, for which Eq. (2-38) isa special case. [The method described bby Eq. 2-39) was used in Example 2-1, part (6)(2).] From another viewpoint Eq. (2:39) can be physically tnlerpreted in the following manner. ‘Ihe entropy tux trom system A plus the entropy production inthe region between A and equal the entropy flux into system B. xample 2-2, Heat transfer occurs between two bodies with temperatures of 300 snd 1000 K. Determine the entropy production associated with « heat wansfer of 100 8, in KK. ‘Model. Both bodies ae of Axed temperature Solutian. ‘The enttopy production associated with hoat transfor between two racer ‘ois is given by Ea. (2-38). in this ease 14 vol 7) Is cay een ht 87 slowed in vale tora 30K, he enopyprton tnpeocies azo. Noe use tnt he answer bc ot um of he ehoges nupy ofthe fwo eat rsern Ta o he bats FB, 39) “San, 572. 100, 100 a, 29 ~ Sm DS = + AM =o aK Fm ater viewpoint the entopy fax fom A of 0.100 WME. plus he eouopy prediction in the epionbewoen an 0.253 WK equal he eno fn Poros une 0.233 IK 2-6 SECOND-LAW ANALYSIS FOR ‘A CONTROL VOLUME, ‘The entropy balance for any closed system has been shown to be (2-36)Advanced Thermals SONDALAW ANALYSIS FOR A CONTROL VOLUME 61 ‘oF on a time basis o am ‘The extension of this latter equation to a control volume may be made by an approach similar to that used to develop the general energy equation for a control volume. In Fig. 2-7 a control mass at time f lies within the small region A plus region CV. Attime 1 + Ar the mass of interest lies in region CV plus the small region B. At these two times the entropies of the contro! mass are Seas = Sa Sev and Semsas = Scvvar + Se Subiraction of the frst equation from the second equation yields the entropy change during the time interval At, namely, Somuesae ~ Seater = Severs ~ Seve + Sa ~Sa ‘To express this equation on a time-rate basis, we first divide by 1, Noting that Sa = misy and Sy = mzs2, we obtain Scmrese~ Sous _ Scvsear~ Seva , aso _ mist AF ~ a ar Ar Inthe limit as Ar approaches zero, the boundaries of the control mass and control volume coineide, and the above equation becomes dSem _ dSev a de + nasa — Hn © FIGURE 2.7 Development of an entropy relation for 3 conta volume. (a) Conte massa ie (@) contol mass atime f* AeAdvanced Thermodynamis for Engineers (62 We socono Low oF tERMODENAMICS For a control volume with multiple outlets and inlets the above equation is written, dom _ dSev “a A, So 8 NS rts — Ss (2- aed -_ ‘The substitution of Eq. (2-27) shown above for dScy1/dr into Eq. (2-40) yields an important form of the entropy balance for a control volume on a time-rate basis. Thar is, 2-4 The quantity @i/; is the rate of entropy transferred through the portion of the control surface where the instantaneous absolute emperature is T,. The value of ‘the suramation can be postive, negative, or zero. Tas noxt two terms account for rates of entropy transfor dic to mass transfor The Binal term represents the mito of entropy generation due to intemal ineversibilities within the contol volume, and can only be positive or zero. Its useful t0 rearrange Eq. (2-41) to find an expression for the entropy generation within a control volume. Thus Dis Daas SS =o 2-42) ‘Tho vast majority of enginsoring analyses are diroctod toward control volumes ‘operating in steady state. This requires that dScy di = 0. Therefore Eq. (2-42) reduces to fev = Sins Dns — SS 0 (oready sate) 2-43) ‘This equation is another illustration that in real processes entropy is not conserved. In steady state mass rates of flow in and out are equal and rates of energy transfer in and out are equal, However, Eq. (2-43) dictates that the net rate of transfer of entropy out of 2 control volume in steady state must be positive for irreversible processes. For those many steady-flow processes which involve only one inlet and ‘one exit the equation for entropy generation becomes bey = ins) (steady state) a4) ‘where subscripts 1 and 2 again represent inlet and exit positions. Upon rearrange- ‘ment the specific entropy change for a steady-flow process with one inlet and one ‘outlet becomesAduanced Thermesiyamics SecOMD LAW ANALYSIS FONE A CURR wine 63 (2 sdev = t & a omev (steady state) (2-45) where the specie etry proncton within the contol volume cv = dcw/th In comparison call at te specificentopy change ofa closed system is Eien by (2~ slow = Sf +oqcu Closed system) 237) ‘The similarity of the tons on the right-hand side of thse lst two equations is pot unexpected The conclusions dawn ear from Eq, (226) regarding the magnitude ad sign on As fr lod yer ee equally valid for a unit net paveng tough a Scadysias conrel volume es eposcnted by Bq. @-43) Thebe ae et w exit cau inerease, decrease, or remain 1, The specific entropy change fiom 2. Because doy can never be negative, the only way that the specific entropy change can decrease is for the entropy transfer out accompanying heat transfer cut of the control volume to be greater than the entropy produced internally by imeversibilities. 3. When internal ireversibilities are present and heat transfer is absent, the spe- cific entropy will always increase from inlet to exit. 4, In the very special case of no heat transfer and no intetnal irreversibilities the pecific entropy will not change: that is, the flow is isentropic It should be recognized that the summation term Q;/7} in Eq. (2-42) might be difficult to evaluate numecically, because the values of Q; and 7; are not known ‘at every position on the control surface. However, the calculation of © Q,/T: ccan be avoided by choosing a system which includes the control volume and any ‘eat reservoirs which might supply or receive heat during a process, including the atmosphere. Figure 2-8(a) shows a schematic of a control volume which ‘exchanges heat solely with the environment at Ty and (arbitrarily) only one other reservoir at Tr. ‘AL any arbitrary position along the control surface we consider a transfer of heat Q; at a boundary temperature of 7). Consider that Qy is transferred ‘reversibly (due to a finite temperature difference) from Tp to T), a8 shown in Fig. 2-8(6), The entropy production associated with irreversible heat transfer was, shown earlier to be given by the sum of the ~Q/T terms for the region of interest. For the small heat-transfer region associated with 7;, Tr, and Qj the ‘entropy production is ve=-).' FL Ge)Advanced Thermodynamis for Engineers 64 Tue sacono Law oF THERMODYNAMICS o FIGURE 28, {0} Control volume exchanging heat solely with the environment and one other reservoir at Ty; (8) heat tasfer between a reservot Ty and small egon oft conta volume a 7, where Q; is measured relative to the control volume. If we now sum over the centie control surface where heat transfer occurs between the control volume and Tr then for n heat-transfer regions along the control surface Noting that Tp is constant, and that SQ, = Qe, we find thatthe summation in the first term on the right reduces to O/T. If we also include those heat- transfer regions between the contro volume and the reservoir To, then a similar term ~Qo/To must be added. (Note that signwise Qx and Qo are to be measured ‘Upon rearrangement 2-46) ‘A more general statement of Eq. (2-46) would be Doo + SSH Annet yt LT where the summation on the right-hand side allows for several J) heat reservours other than the atmosphere. The above equation becomes, on a rate basis,Advanced Thermals SUCONTALAW ANALYSIS OR A CONTROL VOLUME OS 2-47) This is the desired resule which will be used to replace ¥: Q,/T, in Eq. (2-42) ‘The replacement expression now contains «7g, the entropy generation term for the ineversible heat transfer to ot from the Zp and 7; reservoirs. “The substitution of Eq, (2-47) into Eq. (2-42) yields Saas - Die (2-48) Ga = dev tg = er ‘where Qo and Q; are measured relative to the control-volume boundary. Compared to Eq. (2-42). this equation has the advantaze that normally Qo, Q,, To. and T) ‘are known quantities in an analysis. In steady state dScy/dt = 0, and Eq. (2-48) becomes Se Sits Sins 92 imo ceendy oes) — 2-40) a Ty 7; Recall Eg. (2-43). which applies solely to any contol volume with Q, measured relative to the control volume at surface temperature 7), namely, doy = Sas Sts 8 ieady sate 2-43) Anough these later two equations have a similar format, thei usage is quite sitet, Finally, considers contol volume with one inlet (state 1) and one outlet (state 2) and heat is exchanged with a singe-reservoir at Ty (which could be To)- Equation 2-49) bocomes, alter rearangement, ao tow (2-50) “where rer is the sum of the entropy generation due to internal ineversibilities and due to ireversible heat transfer. In addition, s» 51 is the specific entropy change ‘of the mass passing through the control volume, and subscript “R™ represents the single-reservoir condition. Example 2-3. Steam emters a turbine at 40 bars, 500°C, and 140 ms and leaves as a saturated vapor at 100°C and 80 mis. The measured work output is 746.0 kKiikg. The average temperature Ty at the outer surface of the carbine where heat transfer occurs to the environment Is taken a the average ofthe inlet and ext steam temperatures, The potential-energy change is negligible. (a) Determine the specific entropy production within the turbine. in kJ/kg K. (6) Now, enlarge the contol Volume so thatthe ocal environment at 25°C is inclaed. Find the specie entropy ‘production in this case. (¢) Discuss why these answers are differentAdvanced Thermodynamis for Engineers (66 rn secon Law oF teRMODYNAMICS » FIGURE 29 Figure for Example 23 Solution (a) The specitic entropy production oy,cy for the contro! volume with one inlet and one exit is given by Eq. (2-45). On the boss of unit mass entering and leaving the contol volume this equation becomes +3 aT Catv ea ‘The entropy flux at the control surface shown in Fig. 2-9(a) is given simply by 4/T>. because the surface temperature 7, is represented by a single boundary temperature Ty. Thus the preceding general relation is approximated in this ease by ‘The only unknowa in this equation is q, which is found from a steady-flow energy ‘altace mw thy ays BSE From the team tbls we find ht yan hy ae 3445.3 and 26761 Kg, respec: shel. Therefore 2 (807? = 40? a= 7460) + 2676.1 = 345,9)+ OEP 9.6 rg In addition, te specific entropy values atthe inlet and exit are 7.090] and 7.3549 J/kg, respectively. On this basis the spevific entropy production is m.cy = (7.3549 ~ 7.0901) ~ =225 = 0,5168 kite: K (b) When the contol volume is moved sufficiently away from the turbine surface, as shown in Fig. 2-9(b), the value of T, becomes Tp. For this situation the specific entropy production is found wo beAdvanced Thermals SECOND-LAW ANAIYSIS FOR A CONTROL VOLUME. 67 mae = (1.3889 ~ 7.0901) — 0.3688 kg (©) The evaluation indicates that the entropy production increases when the larger control volume is considered. In pat (a) only imeversbilities within the turbine are evaluated. In part (b) imeversible heat transfer between the turbine cover and the atmosphere is also included. Thus the entropy production due 10 heat transfer is (0.3648 — 0.3168 = 0.0480 AJ/kg-K. This sime value is found by employing Eq (2-38). That is, too ve eli 73)” The entropy production due to hea transfer across the fnte temperature difference is only 15 percent of that produced within the turbine. ‘This is not surprising, since the ‘heat loss isomly 4 percent ofthe actual work delivered and the external temperate ‘gradient is relatively small a m7 (0880 biikg °K By an approach similar to that used n See. 2-3-2, iL may be shown that ‘both Eqs. (2-33) and (2-34) apply to a steady-flow (sf) control-volume analysis as well. A combination of the second 1’ ds equation and the basic entropy generation equation for a unit mass, namely, Td dh—odP and Tds = Bay + 50° yields ah Bagns +TRa 4 0dP In addition, for a control volume with one inlet and one outlet the energy equation for steady flow can be writen as Buc + BWepaci = dh + d ke + dpe Since dh represents the same quantity in the two preceding equations, on equating these terms we find that Bwyyax = P80 | vd? dhe t dpe est or noting that 5pay = dP + d ke + d pe from mechanics, we have Swept = P80 + BW sj Rearrangement of the latter equation shows that on a rate basis for steady flow bécy = Pita 2s =0 252) Bwspace = BW (2-53)Advanced Thermodynamis for Engineers ‘These latter two expressions are equivalent to Eqs. (2-33) and (2-34) developed for a closed system. Thus in the analysis of compressors, pumps, and fans, with work input Wopimat ® Wapineey (Compressor, pump, fan) 2-58) and for turbines with work ouput Wrpomat = Wrfoee (turbine) (259) ‘Thus to minimize work input or maximize work output for closed or open sys tems, we must attempt (0 minimize internal imreversibilites, With the general equations developed above, we are now in a position to examine the role of fenirapy production in steady-flow processes. 2.7 ENTROPY PRODUCTION IN SIMPLE, CYCLIC DEVICES A Carnot heat engine, refrigerator, or heat pump is totally reversible, Thus the cyclic system itself, the reservoirs used, and the heat-transfer processes must all be reversible. As a result, there is no entropy production associated with these idealized devices. We now wish to consider heat engines, refrigerators, and heat pumps which are imeversible, and hence have entropy generation during their operation. However, to simplify the analysis, we shall assume that the source ‘and sink for heat transfer are heat reservoirs. That is, the heat source and heat sink have constant temperatures and are internally reversible, Recall that for heat transfer between two systems with temperatures T and Ts, the entropy production 179 is given by Eq. (2-38), namely, oft 4 . oo “SF oly, x) (238) whete Q is taken as positive in value and 14 > Tp. This ieversble heat-transter process is illustrated in Fig. 2-10(a). We shall now apply this information on entropy production de to irreversible heat transfert the stady of imeversible heat engines, refrigerators, and heat purps operating between two heat reservoir Fist, consider the situation where the Reat transfers to and from a cyclic heat engine are reversible but the eyelie system itself is irevesibe. A heat engine schematic is shown in Fig. 2-10(b). The heat transfers Qy and Q are shown to occur across differential temperature differences. However, because the engine itself operates ieversibly, the atua ficiency must be less than that of a Camot engine operating between the same two temperatures For the engine we may writeAdvanced Thermals revrnory PHOBLCTION IN saME CEL URES 6 Ty 2.) Ty thy ~Te> Te o Body Ba th ) » © FIGURE 2-10 (a) Imevesble bet tester from Ty to Ta: (beat engine with reversible eat transfer and reversible engine operon; () eat engie with reversible heat transfer and engine operation, whore T; is measured atthe honndary of the engine The engine is a cyelic device Hence for an integral number of cycles AScuine = 0. Thus Creagice (256) In addition, Qy + Qu + Weer = 0 and ny = —Whr/ Qu. In all three of the preceding equations the sign on Qu, Qz. and Wye, must be supplied as well as their magnitudes. Example 2-4. A heat engine operates between two heat reservoirs, the temperatures of which are 1000 and 300 K. Consider the situation where the eyelic system is als at 1000 an! 300 K while receiving or rejecting heat {recall Fig. 2-10(6)]. In addition, the measured thermal efficiency of the engine is $0 percent. Ifthe heat su the engine during one cycle of operation is 100 kJ, determine the entropy production, in KK, for the eyele. ‘Model, ‘The system consiss ofan ireversible heat engine and two heat reservoirs ‘exchanging heat reversibly ‘olution. There 18 no temperature diterence between tne engine and etiner reser ‘oie when eat is transfered, Hence the het-ransfer processes ae reversible andtheAdvanced Thermodynamis for Engineers 70_Te secowp Law oF THERMODYNAMICS entropy production is zevo for these processes. However, the actual engine efficiency is $0 percent, whereas the Camot efficiency, given by 1 ~ T,/Ty, is 70 percent. ‘Hence the engine operation is internally ieversble. The entropy production asso- ciated with the engine operation is found from Eq, (2-56), namely, Oreaine = For Oy = 100K and 1 = 50 percent = [Wral/ Oy, then Woe) = $0 KS. Prom an energy balance on the eagine, Qz, = 50 KJ. Hence the entropy production for the actual heat engine is - -[1%., = eos ~~ {7000 * 300 0.0667 14/K Figure 2-10(c) illustrates the situation where the heat transfers are irreversible ‘and the heat engine may be reversible or irreversible. Heat transfer Qzs occurs between Ty and Ts. and heat transfer Q, occurs between Tp and T;. Hence the heat engine effectively operates only between Tx and Ty, and not between Ty and T,. Consequently, the sum of the entropy generation terms for the two hheat-iransfer processes and the engine process is Fun = To.rign + eagine + 7.08 Ou , Qu\ (Qu , Qu) (Qe , Ox esr = Bh) eee Several terms in the ahowe oqeatinn will cancel out. However, if left in ite present format, Eq. 2-57) will yield the values of the separate entropy production quan- tities. A comparison ofthese values will show which process contains the largest {or smallest losses. In practice, this would help the engineer to decide which portion of the overall process needs improvement. It is obvious that if « boundary is drawn around the entire heat-engine pro- cess, then On , Qe Te Th This format would be useful in comparing several different heat engines overall, but it gives no information on the contributions of processes associated with the cycle. A similar analysis can be made for refrigerators and heat pumps operating between two reservoirs Example 25. Consider the same pysical situation as in Example 2-4, except that the engine temperature during heat addition is 900 K and is 380 K during hea rejec- siom [recall Fig. 2-%(c)]. The heat engine is considered to be reversible. Determine the entmpy prediction forall the imevorsbilisiee provent in the overall process, imAdvanced Thermals LeeTaorY MROBUEHON W SiMe CLEC eves TH Model. Reversible heat engine and iereversible heat transfers Solution. The thermal efficiency of the reversible heat engine is now based on temperatures of 900 and 380 K and is 61.1 pervent, For the same heat input of 100 J as in Example 2-4 the net work ourput becomes 61-1 kJ and the heat rejection is 38.919. The enuopy production within the reversible heat engine is zero. However, the heat-ransfer processes themselves are ineversible, because a fiite temperature eee ass eens 10-10 cone = -[28) + 32] oon ere In addition, forthe engine heat-ejection process 9, -38.9 350 * 300 So. } = 018s ux Henee forthe overall process, aig = 0.0111 + 0.0185 = 0.0296. IK, The low temperatre heat-tansfer process makes a sizable contrition (62 percent) to the ‘overall entropy production, Example 2-6. Consider the same physical siuation asin Example 2-5, except that the engine ix now ireversible and has a thermal efficiency of 40 perceat. Determi the entopy production forall the ireversibilities present im the overall process, in KK. Model. Irreversible heat engine and heat transfers Solution. ‘The thermal efficieney is now 40 percent. For the same heat input of 100 KI the net work ouypat becomes 40 KF and the heat rejection is 60 KJ. In this situation the entropy production forthe engine is 100 , 60) rage = ~ [900 + FA | = 0.0603 137 The entropy production forthe hea-transfer process to the engine remains the same as in Example 2-5, namely, 0.0111 ki/K. In addition, fo the engine heatejection process ee. =a 330 * 300 Cow = ] = 9.0286 Hence for the overall process awe = 0.0603 + 0.0111 + 0.0286 = 0.1000 KK. “The engine operation in this ease is the major contributor (60 percent) tothe overall, entropy production ‘The analysis of entropy generation in simple refrigeration and heat pump cycles ‘would be similar to that shown above for a beat-engine cycle.Advanced Thermodynamis for Engineers ‘72s Second Law oF THERMODYNAMICS 2.8 ENTROPY PRODUCTION AND FIRST-LAW EFFICIENCIES ‘The first-law efficiencies of several devices were re\ efficiencies can be written in terms of entropy production within the device. This is not surprising, because both first-law efficiencies and entropy production relate reversible and irreversible performances. Recall Eq. (2-51), which applies to a steady-state control volume with one inlet and one outlet: Bw sjun~ T37 + 0dP + dhe + dpe st ‘This equation, then, is combined with the first-law efficiency for various work devices. As an example, cousider a steady-flow turbine for which dhe adiabatic (tirsi-law) efficiency 1, is given by ne when written for a differential change of state. In addition, in the absence of kinetic» and potential-energy changes, 8¥my..s = 0 dP. When Eq. (2-51) is sub- stituted into the above relation we find that _ Dbacy + We _ Téocy + 0dP bie dP For a turbine dP is negative and for any device 3acy is positive. Hence greater intemal jrreversibilitiee lead to larger o valuce and smaller turbine first law off ciencies. Thus turbine performance is directly affected by entropy generation. A. similar analysis would hold for compressors, fans, and pumps. In nonwork devices such as duct flow, nozzles, and diffusers Eg. (2-51) still applies. In the case where shaft work and potential energy change are zero, this ‘equation can be written as ™ dP = ~Téa-dke In the case of internally reversible flow 6c" is zero and vdP + d ke = 0. For ‘example, the drop in pressure in an adiabatic nozzle is responsible for the accel- eration of the flow. For internally irreversible flow through an adiabatic nozzle 60 > 0. Thus kee: = -T60- dP (imeversible nozzle) For a specified value of dP (which is negative) the change in kinetic energy is decreased by the presence of entropy production. In terms of the adiabatic nozzle efficiency 7, we find that these _ ed TS ™ = Thee =odPAdvanced Thermals Hn pamecian ane rinse tiny emeeciRS 73 Like 2 turbine, dP? is negative and 6c" is positive. Thus the presence of entropy production due to internal irreversibilities degrades performance. ‘An interesting application of entropy production isto the behavior of a fluid passing through a horizontal, insulated pipe or duct under steady state. Equation (2-51) ictates in this ease that VdV +T80+0dP =0 (2-58) However, in courses in fluid mechanics the concept of “head loss" he is introduced in terms of a “friction factor” f. The format usually presented is ~odp ~vav = bhp = L048 dP ~ vaV = bhp ~ 208 et Ld ap vav 1 A soar =0 ‘A term-by-term comparison of the above equation with Eq. (2-58) shows that Was D Hence the term T Boy is a measure of the head loss due to internal friction, In the situation where velocity changes are negligible Eq. (2-59) indicates that acy is directly related tothe pressure drop inthe duct. The rate of entropy production inthis case would be given by Tac ohe (2-59) Tbacy =—vdP or ‘This result indicates that the rate of entropy production due to frictional shear stress is proportional to the mass flow rate and the pressure drop. ‘This relationship berween & and AP is clearly shown by employing the ideal-gas and incompressible models for uid flow through ducts. ‘The steady- state entropy balance for adiabatic flow through a duct, based on Eq. (2-44), is Gey = rn(s ~ 51), where state 1 is the inlet. The steady-state energy equation for adiabatic flow through a duct with negligible changes in kinetic and potential ‘energies reduces to fy = ha. For an ideal gas this requires that 7 = T> and that sp — 51 © ~R InP2/P1. Substitution of this result into the steady-state entropy balance shows that — ; Pi ap fey = mR In min in( S ‘When (P ~ Pa) <& P,, the relation In( + x) = x may be used to transform the above equation into, tov =-ne2 ae) cane cHAdvanced Thermodynamis for Engineers 74 Tue secon Law oF THERMODENARICS For an incompressible fluid As = c la(Tz/T;), where the specific heat ¢ is as- sumed to be constant. Also, since fi; = fr, for an incompressible fluid ¢AT + AP = 0, or A/T, = ~cAP/cT, Consequently, E caf. 222) mpi When pAP < ce: to be written as + then the relation In(1 ~ x) = —x allows the above equation mw SP _ fino(P,— Py) Ty T Gey = (incompressibley 2-61) Both Eqs. (2-60) and (2-61) show that gey is a direct function of rit and AP for these models. PROBLEMS 241. Present.a proof thatthe following process is imeversible, A pice of copper is cooled from 100 to 20°C by submersion into a very large body of water 2-2, Present proof that the following process is ireversible. A saturated liguid con- fined to a pston-eylinder device of constant pressure is sted until one-half of it ‘evaporates, 2-3, Present a proof that the following process is imeversble. A gas expands slowly ‘through a small hole from one chamber into another chamber where the pressure initially s considerably lower. 24, A vessel intially contains 5.0 kg of liquid water and 2.0 kg of ice at O°C. Energy is added until the ice has just melted, The temperature at the boundary where hheat tamsfer occurs is taken to be the system temperature during the process. The enthalpy of meling is 333.5 ki/kg. Consider the following processes used to melt the ice. ‘8, Heat is added from the environment at 20°C. Determine the entropy flux and the total entropy generation, both in KK i. Heat is added from a reservoir at 727°C. Determine the same quantities as in part (a). . Padle-wheel work is used to change the slate. Determine the total entropy production forthe process, in VK. 4. Comment on the relative degree of ineversbility forthe three processes, 2-8. A piston-cylinder contains 0.10 kg of saturated liquid water at 10 bars. Energy is added until the liquid has just evaporated. The boundary temperature where heat transfer occur is taken asthe saturation temperature of water at 10 bars. Consider the following tree processes, 2, First, heat is added fiom a reservoir at 227°C. Determine the entropy Aux for {he sic and the toial entropy production, both in KI/K. b. Second. heat is added from a reservoir at 2000 K. Find the same quantities requested in part (2).Advanced Thermals rrowuens 7S e. Thin, the energy is added by electrical work on a resistor within the cylinder, Deternine the entropy generation within the fluid and the toal entropy production forthe process both in K/K. Fourth, one-alf the energy required comes fom heat addition at 227°C, the other half comes from electrical work input. Find the entropy production due to the electrical work aad the tral enopy production for the overall process, both in IK. ‘e. Compave the relative imeversibilty of the three processes. 246, A piston-eylnder contains 1 L (liter) of saturated liquid R-134 maintained at 6.0 ‘burs, Energy is added until one-alf the liquid has evaporated. The boundary tem= perauure where heat ansfes oocurs is taken as the saturation temperature of the -134a at 6.0 bars. Consider the following three processes. Firs, heat is added from a reservoir at 127°C until the required liquid has ‘evaporate, Detertine de entopy fa fr tke R-La ad the atopy production for the hea-iransfer process, both in JK. bi. Second, the hest added is from a reservoir at 600 K. Find the same quanti requested in par (3) "Third, one-half the omergy raquied ic added by heat trancer from the 127°C reservoir, whereas the other half is added by electrical work on a resistor within the cylinder. Determine the entropy production within the R-L34a and for the Iheavransfer process, both in WK. 44. Compare the total entropy production forthe three processes. 2-7. A closed rigid tank contains 0.10 kg of ai intially at 1 bar and 350 K. Energy ‘is added until the temperature reaches 400 K, Consider the following metbods of energy sddition. ‘a. Heat is added fiom a reservoir at $00 K, and the system remperature where heat transfer occurs is $00 K. Find the entiopy production forthe ai, in 37K. be The same situation as part (a), except that the temperature at the boundary ‘where heat transfer occurs is the same asthe air temperature within the system. ‘throughout the process. Find the entropy generation for both the air and the ‘overall process, in J/K. ce The energy is added in the form of paidle-wheel work. Find the total entropy ‘generation forthe process, in J/K 2-8. Carbon dioxide (CO2) at 110 kPa and 290 K is contained within a constant-pressuce jston-cylinder assembly with an initial volume of 0.020 a, Energy is added until the temperature reaches 380 K. Consider the following processes. ‘4, Heat is added from a reservoir at 300 K, and she system boundary temperature is the same as the gas temperature throughout the process. Find the entropy change andthe entropy fox forthe gas, bot in MK. b. Calculate the entropy production for an enlasged system which includes the piston-oylinder device as well as the reservoir, in VK. «, Caleulate the entropy production of the gus and the total valve if the system boundary temperature throughout the process is 400 K, in IK. 4. The process is repeated by using electrical resistor work instead of hea alton. Find the tal entropy production. in IK. Compare the relative reversibility of the processes. . A closed rigid tank with a volume of 2m contains hydrogen gas intially at 320 K ‘and 180 KPa, Heat transfer from a reservoir at 500 K takes place until the gs temperature reaches 400 K.Advanced Thermodynamis for Engineers 76 we secon Law oF nERMODENAMIES 210, 2a. 22, 213. 2a. 26. ‘8. Calculate the entropy change and entropy production fr the hydrogen gas during the process, both in JK. ifthe boundary temperature for the gas is the same as the gas temperature throughout the process. bi. Determine the entropy production, in KNK. for an enlarged system which in- cludes the nk und the reservoir «e Explain why the entropy production values differ for parts (3) and (). 4, Find the entropy production forthe gas and the tral value, in RIK, ifthe system, boundary temperature is 480 K throughout the process. ‘The hyciogen gas process is repeated, but paddle-wheel work is used instead of heat transfer. Celeulate the entropy production in this case £. Compare relative ireversibily of processes (b). (8), oF (). A LS block of copper at 100°C and a 1.0-kg block of aluminum at 27°C initially sre isolated from each other and from the local environment. They ate then placed 1m thermal cootact with each other but ae sill isolated from the eoviroument. Determine ‘2. the equilibeium temperature in degrees Celsius '. the entropy generation forthe process, in KIK. A rigid insulated tank is divide into two compartments by 2 noninsulated partion. Inially, 0.40 kmol of COz is rapidly introduced into one compartment at 4.0 Dus and 300 K. AL the same time 0.10 kmol of CO is induced into the other ‘compartment at 1.0 bar and 500 K. Determine (a) the equilibrium temperature, i Kelvins, and (b) the entropy proiction for the overall process, ia KJIK. Use CO and CO> tabular data. AA piston-cylinder device maintained at a constant pressure of 0.10 MPa contains nitrogen gas. The gas is cooled from 420 to 310 K. Compute (a) the heat removed, in Kkg, and (b) the enteopy production for the heat-transfer proces, in kl/kg - K. 1 the temperature of the envionment is 22°C. Use the nittogen idedl-gas table for data, Nitrogen flows steadily and isorhermally through a duct at 400 K such that the heat transfer into the fluid is 5.56 KIAg. The inital and final pressures ae 2.40 and 1.80 bars, respectively, and the diameter ratio D,/Dz for the duct is 1.40. Determine () the entropy generation for the fluid, in ki/kg-K, and (b) the inlet and ei velocities ofthe fluid, in mvs, if the potentalenergy charge 1 negligible ‘Air flows isothermally at 60°C through a constant-area duct such that che entropy increase due solely to internal ieversibilties is 0.0548 KS/kg K. Determine 4 the heat added or removed, in Ki/kg, if the initial and final pressures are 400 and 320 KPa, respectively ‘the inlet and exit velocities, in avs Oxygen flows steadily and isohermally at 300 K through a constan-area duct such that the entropy production due to inerualireveribiltes i 0.0995 K/kg-K. Find a. the heat added or removed, in kik, if the initial and final pressures are 3.0 and 2.4 bars, respectively ‘the exit and inet velocities, in mvs ‘The entty pwedoetion ic 1406 /kg-K when COs ie dotted adiabatically fom, 8 bars. Determine (a) the final pressure in bars and (b) the ratio of inet to outlet wea if itis assumed thatthe inlet and exit velocities ate identical,Advanced Thermals 2a. 28. 29. 2a. 222. 223. 2M rmowuems 77 ‘The entropy production @ for nitrogen, an ideal gas, is 0.360 KJ/kg K when itis throttled from an initial pressure of 400 KPa. Deteriine (a) the final pressure, in kilopascals, to which the gas i throtled and (b) the ratio of the inlet to outlet area if the inlet and exit velocities are identical Oxygen, sn ideal eas, is thotled from 6.0 to 3.0 bars. Determine (a) the internal entropy production forthe fuid, in kJ/kg.°K, and (b} the ratio of the inlet v0 ule area ifthe velocities are small, but ¥2/Y = 2// Refigerant-134a enters a compressor aa saturated vapor at 24 bars. At the ext the pressure is 7.0 bers, and the entropy has increased by 0.0645 Ki /kg -K under adi ‘atic conditions, The changes in kinetic and potential enetgies may be neglect. (a) Determine the work input reyuired, in Kitkg. (b) For the same initial cond tions and the same final pressure, the compressor is run without insulation. The entropy production is assumed to remain the same as in part (a). However, the en- ironment at 22°C enperiencss an enttopy inteare of 0.0190 IJ/K per kilogram of R-134a, Ifthe work input required in this case is found tobe 41.77 kUkg, determine (b) the heat transfer, in Kkg, (c) the final temperature, in degrees Celsius, and () ‘the enttopy temafer dic to heat tranefoe fe R-1da, in EI/kp » K Stoam enters a twine at 120 hare and 440°C and espana to har. At the exit the ‘entropy is 0.650 kJ/kg K greater than at the inlet. The process is adiabatic and ‘changes in kinetic and potential energies may be neglected. a. Determine the work done by the scam, in k/kg 1b. Now, forthe same inicial conditions and the same final pressure the turbine is rum ‘without insulation. Its found thatthe entropy increase of the steam is now 0.600 Kl/kg K, and that the heat transfer from the steam oceurs to the enviroamenty which is at 300 K, The entropy change of the environment is 0.0850 KI/K pet kilogram of sear. Determine the heat transfer and the work output fr the steam turbine under these new conditions, in Kirke. ‘Steam enters a turbine at 100 bars and 400°C. At the ext the pressure is 1.0 bar ‘and the entropy has increased by 0.600 J/kg” K under adiabatic conditions. The ‘changes in kinetic and potential energies may be neglected. (a) Determine the work, in Ki. For the same initial conditions and final pressure the turbine is now run ‘without insulation. The entropy production duc to internal irreversibilities is assumed to be the same as in part (a). However, the environment at 300 K is found to have an entropy change of +0.0800 Ki(kg steam) K. Also, the entropy change of the ‘seam de to heat exchange with the envigonment has an absolute value of 0.0460 J/kg: K. (b) Determine the quality of the steam at the turbine outlet, and compare to the ansver from part). Also, (¢) determine tho heat transfer tothe enviroament, in kilkg steam, and (4 find the amount of work output of the turbine, ia Rik, and ‘compare to pat (a. ‘Consider Prob, 4, Determine the value of the entropy production fo the process, in /K: min. ‘Water and steam eater an insulated mixing chamber in steady flow. The liquid water enters at 20°C and 3 bars with a rate of 100 kg/min. The steam enters at 320°C ‘and 3 burs, and the mixture leaves the chamber at (a) 130°C and 3 bars and (b) at 3 bars as saturated vapor, Determine the value of the entropy production for the processes, in 1J/K *min (see Prob. 1-18). Consider Prob. 1-5. Determine the value of the entropy production fr the process, fn kJ/K min, ifthe steam enters at 200 kg/min.Advanced Thermodynamis for Engineers TH We secoxD LAW OF THERMODYNAMICS 2-25, A heat pump unit operates between two beat reservoirs with temperatures of 270 and 330 K. The heat pump itself has @ temperature of 288 K during heat addition from the 270 K reservoir and a temperature of 350 K during heat rejection to the 330 K reservoir. The COP of the sctual unit is 3.40, and the heat wransfer rate ‘rom the 270 K reservoir is 2000 ki/min, Determine the entropy production rate, in Kd/minK, for a. the heat pump unit itself Di. the low-temperature heat-transfer process ‘the high-temperature heattransfer process 4d. Which process has the Larges irreversibility? Now, forthe same temperatures and a heat-ransfer rate of 2000 ki/min, reduce the actual COP to 3.10. Again, determine the entropy production rate for the meftigeration unit eit the low-temperature heat-transfer process . the high-temperature heat transfer process |b, Which process now has the largest ireversibility? 2.26. refrigeration wait operates betwaon two heat rsarirs with trmperatiee of 240 and 320 K. The refrigeration unit itself has s temperature of 230 K during heat addition from the 240 K reservoir and a temperature of 340 K during heat rejection to the 320 K reservoir. The COP ofthe actual unit 2.00, and the heatransfer rte from the 240 K reservoir is 1000 kJmin. Determine the eatopy production mite, K/min K, for a. the refrigeration unit itself i. the Low-temperature heat-transfer process ‘the high-temperature heat-transfer process 4d. Whieh process has the largest ereversibiity? Now, for the same temperatures and a heat-ransfer rate of 1000 ki/min, reduce the ‘actual COP to 1.50. Again, determine the entropy proiction rate in kJ/min-K for & the refigeration unit itsait the low temperature heat transfer process 1 the high-temperature heut-transter process 1h, Which process now has the largest ireversibility? 2:27. A heat engine operates betweon (wo beat reservoirs with temperatures of $60 and 280K. ‘The heat engine ise? has a temperaiure of 560 K during heat ation from the 560 K reservoir and a temperate of 280 K during heat rejection to the 240 K reservoir. The thermal efficiency ofthe actal unit is 0.40, and the heat transfer rate from the $60 K reserve is 1000 k¥/min, Determine the entropy production rte, in k3/min K, for (1) the heat engine itself (2) the low-temperature hest- transfer process, and (3) the high-lemperatae healtranser proces. bb. Now. forthe same reservoir temperatures, Rea-taasfer rate, and engine thermal elicieney the engine itself receives heat at S40 K and rejects heat at 300 K. As before, determine the entropy proiction rate for (1) the heat engine itself, (2) the low-temperature heataransfer process, and (3) the high-temperature heat-iransfer process. (8) Which process has the largest ineversibiiy?Advanced Thermals nerexrvees 79 . Finally, for the same reservoir temperatures, heatransfer rat, and engine fem- peratures cited im pat (b) the thermal ficiency 1s increased t0 0.42. For these Conditions, determine the entopy production rate for (1) the heat engine it Self, (2) the low-temperature hea-transfer process, and (3) the high-temperature hheat-transfer process. (4) Whieh process now Ini the largest irreversibility? 2.28. A supply line is attached wo the bottom ofa vertical piston-eylinder apparatus which REFERENCE! initially has the piston touching the bottom of the cylinder. A compressed ideal fas at reservoir conditions of (Zp, P) is slowly almited to the cylinder through 4 valve, which lowers the pressure Pz. The pressure P, is maintained constant ‘within the cylinder throughout the process by the weight of the piston and the atmosphere acting om the outside of the piston. The cylinder is not insulated so that the temperature withia the apparatus remains at Tp. Fora contol volume consisting ‘of the gas within the cylinder and the supply line containing the valve, determine {@) the total heat interaction between the system and the envieonment, in J. and (6) the entropy generation, in JK, forthe following conditions: By = $ bars. Py = 2 bars, Vag = 1.0 L, and Ty = 300 K. ‘Camot, 5. Rfletions om the Motve Power of Heat and on Machines Fited ro Develop This Power, Bache, Pas, 1924; sho Reflections on the Motve Power of Fite and Other Papers Dover. New York, 1960. ‘Thomson, W.. “On the Dynamical Tory of Heat, with Numerical Ress Dedvced from Mi Joules Bguvalent of « Thermal Unit, end M. Regnauls Observation on Steam,” Trans. R. Soc. Edinborg. 1831 . Planck M., Teaie on Thermodynamics, de trated by A. Opa, Dove, New Yook, 165 (Grst Geman ein 1897). Matopoaion, GN and 1M Konan, Principles af General Thermodmamis, Sohn Wiley & Sons, New York, 196. CCaraibéodory,C, "Grundlagen der Thermodynamik,” Math, wn, 67:35, 1809 “emnansky, M. W., Heat ard Thermodynamic, 5th ed, McGraw-Hill, In. New Yor, 1968. Tandsere, ®."A dedcton of Corathéodorys ripe fom Keli’ principle,” Nawre Loader), 201485, 1964 Callen, Herbert B., Thermadgnamic, John Wiley & Soos, New Yor, 1960. Bejan: A. Abanced Engineering Thermodynamics, Chap 2. John Wily & Sons, New York, 1988Advanced Thermodynamis for Engineers CHAPTER 3 AVAILABILITY ANALYSIS ‘This chapter isthe first of four chapters inthis text which are devoted to the study Of availability or exergy concepts. In this chapter we shall define and apply the ‘concepts to processes involving closed and open steady-state systems, 31 INTRODUCTION ‘The first law of thermodynamics, when expressed as a conservation of energy principle, is concemed with the quantity of various forms of energy. From an engineering viewpoint a quantity of energy also has quality. Quality is used in the sensc of “degree of usefulness” to society. Changes in systems are brought about by heat and work interactions. Observations of past engineering achievements indicate that work interactions are far more important than heat interactions in bringing about changes of state. Since work interactions have a higher degree of “usefulness,” it may be said that such energy forms are of a higher quality than ‘heat interactions, Even the second law places a higher standard on work than on heat. Work is completely convertible into heat, but the conversion of heat into work by a cyclic device is highly restricted. Thus not only is work more useful ‘than heat, but it is also more difficult ro obtain in many instances, This measure of “usefulness of energy” may be applied to forms of energy in a given state, as well as to energy transformations. The capacity of a given ‘quantity of energy to produce work is accepted as a meaningful measure of the ‘quality of that energy. In a broad sense, then: ‘The quality of energy is the potential of that energy to produce useful work.Advanced Thermals wenmovcenne 81 ‘The useful work associated with a quantity of energy, called the work potential of that energy, requites a datum for its measurement. This datum is usually taken to be the lacal environment. As a resul ‘The work potential of a given quantity of energy is defined as the maxi- mum possible useful work that can be obtained from that energy in a giver Whenever the work potential of a given quantity of energy is reduced during « process, the energy is said to have been degraded. Thus the first and second laws become statements of the conservation and degradation of energy and take on the following format. Every time energy changes form or is transferred from one system to another: The total amount of energy is constant (first law). ‘The potential for producing useful work is redhced forever (second law). ‘Thus during energy tansformations and transfer, energy is both conserved and degraded. It is this potential to do useful work for society that determines the ‘quality of energy. Energy conservation typically means reduction in energy us- ‘age, OF equal importance is the nced to reduce the degradation of energy during its use Note thatthe first and second Iaws cited above ate both expressed in terms of energy. This type of formulation is deliberate. If we wish to have a quantitative ‘measure of the Work potential of a system m a given state of the change in work potential during a process, we must simultaneously apply the two laws. This is quite different from many introductory discussions of thermodynamics, where the two laws are commonly used as separate steps in an analysis. The concepts in this chapter will help Ge together many apparently unrelated ideas. Engineers use thermodynamics to develop energy processes. Many of these processes require the use of work interactions. Among the major goals of engineering thermoxynamics ‘To optimize methods for converting various forms of energy into work ‘To optimize the use of work interactions to bring about desired results ‘To minimize the loss in work potential of a system even in the absence of work interactions ‘The purpose of this chapter is to quantify the general techniques for optimizing energy processes. As we combine these laws into a single relationship, we shall derive a general solution and then proceed to illustrate specific applications 10 ‘eontrol-mass and control-volume analyses.Advanced Thermodynamis for Engineers 82 svaLapmry anatysts 3-2, REVERSIBLE WORK, AVAILABILITY, IRREVERSIBILITY, AND SECOND-LAW. EFFICIENCY In this section we begin by developing a general equation for evaluating work interactions in the presence of irreversibilities. This will enable us to quantify the concept of work potential for closed and open systems. The first law contains a term for work, but there is no energy term which accouats for ireversibililes, The second law contains a term for imeversiblitis (the entropy production or generation term), but no term is speciically written in terms of work. In order to develop an expression directly relating work to enttopy generation (or ieeversibil- ities), we combine the frst and second laws through common terms. Figure 3-1 illustrates a general control volume with multiple inlets and outlets for mass flow. In addition, heat Qo may be exchanged with the atmosphere at Ty, as well as beat quantities Q, with j additional reservoirs at temperatures 7}, ...,;. The total heattransfer cate Q's piven by Q = Qo + S: Qj. Finally, work interactions may also occur actoss the boundary. The term Wree represents the sum of all possible work effects, such as those due to a volume change, shea, eleetrcal effets, and others, As shown in Fig. 3-1, part of the volume change may be done against the aumosphere at Py The general conservation of energy equation forthe control volume in Fie. Sis dEex Oia + Eb F aa) Soli E+ ge =x (40) Aimowpere aT Py FIGURE 3.41 Schema fo the development ofthe Work potential for a procesAdvanced Thermals [EVERSIBLE WORK, AVAILABILITY, IRREVERSIBILITY, AND SECOND.LAW EDRICIENCY 83 By rewriting @ as a sum of terms to the various reservoirs, we can write Eq. (ray 60+ 7 The data points for the velocities and the elevations and the reference state for the enthalpy (or the internal energy) must be the same for the inlets and outlets. Since the work potential is measured in terms of useful work, Woaa. We must correct Whe by the work done against the atmosphere, namely, by Pod (Vol)/ dt. That is, ¥ awed) Waa = Wor + Pp | 2222" 3-2) a) er G2) {i addition, the form of the entropy balance appropriate here is Bg. (2-48), namely, fg = Bey y= SO Sine Ss & oe ->¥ (2-48) ‘We shall now use the above three equations to develop relations for Wax Un der actual and reversible conditions, in terms of specified property values, mass flow rates, reservoir heat-transfer rates, and the environment temperature Tp and pressure Po. 3241 Reversible Work In order to combine the first- and second-law statements, we must recognize an important engineering concept. Although the physical quantities cited above may be fixed by the designer, the heat-transfer rate Qo to or from the atmosphere is arbitrary. It is not under the control of the design engineer but varies as W changes to satisfy the first law, Hence it is justifiable to eliminate Qo between Eqs. (3-1) and (2-48) while also substituting Eq. (3-2), The important result is HEL RV Tae 5 Sa Woes z =a (t+ +52 -m)-> Ss 6, ~ B+ Po 63 where the direction of the Qj terms again is measured relative to the control surface. This is a general equation for the rate of actual useful work (power) associated with a control volume and the heat reservoirs with which it interacts. Although Oo does not appear explicitly in the equation, heat transfer to or from the environment at To is automatically included. Again, the summation sign in front of Q, allows for j possible heat reservoirs at Tj. The term ote: includes entropyAdvanced Thermodynamis for Engineers 840 svastamury avatysts ‘generation within the control volume as well as that associated with irreversible heat transfer. ‘Similar to the development in Chap, 2 of relationships between dey and Scv/ dt, Eq. (3-3) can also be written solely in terms of interactions at the control surface. To obtain this format, we write Eq. (1-40) for the conservation of energy as SOit that She + echo Frejn- 4% an where Q is expressed as a sum of heat interactions 5: Q, at the control surface, rather than in terms of heat interactions to or from reservoirs at Ty and Tj. The appropriate entropy balance solely for the control volume is Ea. (2-42), namely, ev Se + Dae Lie SH 42) Since o does nt appear in either ofthe above two equations, a diferent strategy rust be used o combine the equations, The simplest procedure is to multiply Eq. (2-42) by To and to subirt the resulting equation ftom Eq, G4. The desired result is Waeru dE + PoV — ToSdev a ve SET Salis Fae ter “Safer Boer) S0(1-BJe rier os) Equation (3-5) expresses @ in terms of (; at sections of the control surface at T;, rather than the parameters Oo and >: Q, used to develop Eq. (3-3). These later ‘quantities represent the overall heat-ransfer rates associated withthe environment at Ty and those reservoirs at 7). Recall from Sec. 2-6 thatthe relation between entropy generation and work: effects for @ control volume on a time basis is given by Baroy = PWisas— Pep (2-52) F Whea dey is zero, the process is internally reversible and Wapare = Ware. Tas the optimum or reversible value forthe rate of useful work, in terms of Eqs, (3-3) and (3-5), is given either by ooAduanced Thermesiyamics [REVERSTELE WORK, AVAILABILITY, IRREVERSIBILITY, ARD SRLUND-LAW anHICNCY 85 dE + PoV ~ ToSov - « v Dials Yt ee Tos) on We ~ Sm Fae ms) Sait Equation (3-6) applies to a control volume and the reservoirs with which it in- teracts, On the other hand, Eq. G-7) applies solely to the control volume of inerest. The last term in Eq. (3-7) may be difficult to evaluate accurately, be- cause it requires knowledge of Q; ata portion of the control surface at temperature T,. Nevertheless, itis an important result, since the reversible work is expressed solely in terms of changes within oF atthe boundaries of the system. A major goal of the next three seetions is to replace the fist four terms in Eqs. G-3), 3-5), (G-6), and (3-7) with some form of an availability function ‘The numerical evaluation of reversible work depends on the valves chosen for To and Pp. A logical choice for (T, Pa) are those values traditionally associated with the standard armosphere, namely, 25°C and 1 atm, For comparative purposes itis recommended that Ty = 298.15 K and Py = 1.01325 bars = 0.101325 MPa (3-8) be regarded as the standard environmental state. Values of To slightly from 25°C are frequently used in practice 3.2.2 Availability or Rxergy In the preceding section equations were developed for the reversible work asso- ciated with systems undergoing specified changes of state and exchanging heat with the environment or other heat reservoirs. It is useful to reformulate these ‘equations in terms of the availability functions for closed and open systems. To this end it is necessary first to determine the work potential of a system at a given state as it proceeds toward a state of equilibrium with the environment while ex- changing heat solely with the environment, Once the system and environment are in equilibrium, no further change of state of the system can occur spontaneously, and hence no further work is performed, Hence the above described process leads to the maximum reversible work or work potential associated with the state of a system. When a system and its environment are in equilibrium with each oth the system is said to be in its dead state, Specifically, a system in a dead state is in thermal and mechanical equilibrium with the environment at To and Po. The hhumerical values of (Tp, Po) recommended for the dead state are those of the sian- dard environmental siate discussed earlier, namely, 298.15 K and 1.01325 bars (atm), Additional requirements for the dead state are that the velocity of a closed system or fluid stream be zero and that the gravitational potential energy be zero. This latter requirement is fulfilled by arbitrarily setting some elevation onAdvanced Thermodynamis for Engineers ‘earth, such as sea level or ground level. as zero. These restrictions of temperature, pressure, velocity, and elevation characterize a resiricted dead state associated ‘with thermomechanical equilibrium with the atmosphere. It is restricted in the sense that chemical equilibrium with the environment is not considered. That is, the control mass is not allowed to pass into or react chemically with the environ ‘ment. The work potential of a system relative to its dead state, which exchanges heat solely with the environment, is called the thermomechanical availability oF ‘exergy of that state The methods for evaluating the availability of closed and open steady-state systems, as well as for heat-transfer processes, are presented in several of the following sections. The availability transfer associated with a work interaction is immediately obvious. Work interactions by concept are reversible at the point ‘where they oceur at the boundary. Consequently, the availability ansfer assuciated, with the transfer of work (excluding work against the environment) equals the value of the useful work itself. 32:3 Irreversibility (OF major concem to engineers is the loss in capability of producing work (or the increase in required work input) when irreversibilities are present. One method of ‘measuring such losses is through the concept of “adiabatic efficiencies” for work devices, which frequently are termed “first-law” efficiencies. A more fundamental ‘measure of the loss in work capability of a system (relative to its local environ ‘ment) as a result of a process with specified end states is the difference between the actual work and the reversible work. On the basis of Eqs. (3-5) and (3-7) this irtetence, Wa ~ Wiee, 10F & control volume on a rate basis is given by Woes ~ Wrev = Wact ~ Wiew = Todtey = 0 69) ‘Tais equation indicates that when any system changes state ireversibly, the work capability of the system is reduced (destroyed) at a rate proportional to the rate of entropy generation within the system. (This proportionality historically is known a the Gouy-Stodola theorem [1, 2].) Equation (3-9) may be rearranged into the format Whe = Wiey * Teste Since Gcy = 0, we can restate the inequality between Weer and Woey, presented ‘earlier as Eqs. (2-35) and (2-54), in the following ways: War = Woes Wace = Weer, and Wace = Wasa G-10) Hence the presence of irreversibilites leads to a reduction in output or an increase {in inpot when an actual process is compared to a totally reversible process between the same end states. ‘The quantity of work capacity of a system destroyed or lost during a process is defined as the irreversibility 1 of the process. It is a measure of the availabilityAdvanced Thermals AEVERSINLE WORK, AVAILABILITY, IRREVERSIRILTY, AND SECOND LAW EFFICUENCY 87 for exergy loss due to internal imeversbilities. With references to Eq. (3-9), the inveversibility / on a time-rate basis for a control volume is fey = Wher — Wow = Woes ~ Wan = Tore = 0 Gap For a vast majority of control-volume analyses there is no change in volume. Hence the use of “useful” as a subscript on W is redundant, and it is usually ‘omitted. For a closed system on an extensive basis Tess = Woes ~ Wev = Wats ~ Weve = Torew = 0 B42) and on a unit-mass basis, where {= I/m, feat = Wet — Wrev = Waar — Weevs = Toorem = 0 G13) The parameter J is also known as the lost work, Wig. The imeversibilty of a process, like heat and work, is a function of the path of the process, that is, the design and operation of the system. The parameter J is shown schematically in Fig. 3-2 on the horizontal work-transfer rate axis. Note that Was always lies to the right of Whey so that 1 is always positive as required by Eq, (3-9), The ‘major purpose of an availabilty analysis is to detect and evaluate quantitatively the imeversbilities of a process. Such an analysis could them indicate areas for thermodynamic improvement of the process. If we include external reservoirs and the environment in our system of interest, then Eg. (3-11) takes on the format digg = Woes ~ Weer = Toshi = Tol@ey + 0) = 0 Similar to the control-volume analysis above, J and o in Eqs, @ 12) and (3 13) ‘may refer to the control mass alone, or could include the heat-iransfer processes as well. Thus the concept of irreversibility can be applied to a control volume of ‘control mass alone, or can be extended to include other interacting systems. 3-2-4 Second-Law Efficiency or Effectiveness ‘The first-law efficiencies 1 of some common devices were reviewed in Chap. 1 ‘These expressions are ratios of selected energy quantities. In the context of this, Work out devices <<} Work input devices lustration ofthe ineversibity 1 in terms of reversible and actual wav values Zor work-prodcing and absorbing deviees,Advanced Thermodynamis for Engineers chapter the usefulness of energy is more appropriately described by its exergy or availability. Since availability has its origin in the second law, a performance parameter for a process based on availability concepts is known as a second: law or exergetic efficiency mu. ot as a second-law effectiveness, or simply as an effectiveness ¢. (Both symbols are in current use, among others.) first-law efficiency gauges how well energy is used, whereas an effectiveness indicates how” well exergy or availability is used. Both concepts are important in thermodynamic analysis, First- and second-law efficiencies are different in one other important re- spect. The first law is a conservation principle, and frst-aw efficiencies tend 10 fall into two general categories. Equipment firs-law efficiencies compare actual energy changes to theoretical energy changes under specified restrictions. Exam- piles include turbines, compressors, nozzles, and pumps. Cycle first-law efficien- cies compare desired energy output to required (costly) energy inpot. Thermal efficiency and coefficient of performance (COP) are typical examples. On the ther hand, entropy and availability feom a sevond-law viewpoint are noocon- served propertics. In the presence of ineversibiliies the wial euwpy ineeases ‘and the total availability decreases. The former effect is measured by the entropy production or, and the latter effect is measured by the irreversibility 1. Hence secondslaw efficiencies measure losses in availability during a process. One typi- cal definition of the second-law effectiveness € is availability destruction and losses availability input ‘availability in where losses imply nonusefil Kausters acivns Ue boundary. A secon appro, especially useful for steady-state devices, is rate of availability (exergy) output “Tate of availability (exergy) input The second law stresses the fact that two forms of the same quantity of energy may have quite different availabilities. Thus energy is “weighted” accoed- ing to its availability. Unlike a first-law efficiency, an effectiveness accounts for losses in work capability daring « process. Note, however, that the definitions of € given above are quite general. In specific applications one must still decide ‘what is the desired output, what is regarded 2s input, and what is counted 2s a loss. In later examples we shall demonstrate that different decisions about these ‘tems lead to different expressions for the effectiveness of a given process. Hence different € values may exist for the same data, is not a question of which value is better, or correct. It is a matter of consistency when comparing sets of data Fortunately, the availability balances for closed and open systems are good guide- lines for establishing appropriate second-law efficiencies. In subsequent sections Siscussions and examples will tlustrute the evaluation of the effectiveness € OF ‘my for a variety of systems.Advanced Thermals AVAILARILTY TRANSFER ASSOCIATED WiTH MEAT TRANSFER, 89 3:3 AVAILABILITY TRANSFER ASSOCIATED WITH HEAT TRANSFER Entropy transfer associated with heat transfer Q; across a system boundary at 7; is represented by the quantity Q;/7). A transfer of availability is also associated with heat transfer. To derive this relation, consider Fig. 3-3, which shows heat transfer 8Q, occurring for 7; > To, where 7, isthe temperature at the boundary of fa system, The availability associated with 80, is the reversible work obtainable as the heat is transferred 19 the dead state. To produce work, 6Q; passes through @ reversible heat engine which rejects t0 Tp. Using an overbar to designate quantities relative to the engine, we find the frst and second laws to require that 80; _ 800 TT 800 and Weg ev = 80, Sign convention requires that 5Q, = —8G,, where 8, is measured relative 10 the eyttem at T;, A combination ofthese reliions yields ty a) Ga) Bing = 0 ‘The right-hand side of this equation, then, is the availablity transfer associated with heat transfer 8Q, as it crosses the system boundary at 7). This same result is obtained if the directions of 6Q, and 6Qo are reversed and T) < Tp For a finite heat transfer Q, occurring at boundary temperature T; the above ‘equation becomes Wau = 01(1- F) where p,, defines the availabilty ransfer associated with heat transfer Qi at boundary temperature T;, ( willbe the general symbol forthe availabilty of an extensive closed system; see Sec, 3-4.) For the more general situation where both ou Gas) on FIGURE 33 associated with heat tueAdvanced Thermodynamis for Engineers 90 avsitamtiry axatyss Q; and 7; vary along the boundary of the system (recall Fig, 3-1) a summation of terms must be considered. In this situation Eq. (3-15) becomes t= S0(-8) ce where ©g is defined as the total availablity transfer associated with the heat twansfer quantities Q, which occur at boundary temperatures T;. The rate of avail- ability transfer associated with heat transfer at a boundary is given simply by y= S0,(1- a) G17) ‘ihe term on the right of Eq. (3-17) has appeared previously in Eqs. (3-5) and B-7) for Wary and Wo, in the preceding section. A special application of Eq. (3-15) is to the availability transfer to or from 4 single thermal reservoir at 7; = Tx, where Tp is constant and uniform. Since @; = Qp in this case, the equation can be written as on Oa(t~ 72) ermal rsersir G18) where gg is defined as the availability of heat transfer Q¢ to or from a reservoir at Tp. Note that one does not associate availability transfer due to heat transfer at the boundary of a reservoir at To. If j reservoirs are under consideration, then Eq, (3-18) can be expanded to mass and rate formats such as, G19) Which define the parameter: Pg ;. The last term of Eq. (3-19) on arate basis ‘has previously appeared as a term in Eqs. (3-3) and (3-6) inthe preceding section. ‘The format of Eqs. (3-16) and (3-18) is not surprising. Both equations represent the work of a Camot heat engine rejecting to the atmosphere at 7. (Note that the ireversibilty of any thermal reservoir is zero, because by definition Such a reservoir is internally reversible.) An important point must be noted with respect to Eqs. (3-16) and (3-18) If the system temperature is greater than Ty, then the system gains availability when heat is added, and vice versa. However, it the system temperature is fess than To, then the system loses availability when heat is added and gains availability when heat transfer is out. That is, the energy flow and availability flow are in opposite ditections in this latter case. This effect is important in the study of refrigeration processes. In an internally inreversible process dS ¥ 80/T. In addition, when an itreversibility exists within a system, the temperature T of the system may bbe undefined. In this case, for either closed or open systems, Eq. (3-16) for theAdvanced Thermals AVAILAMIIFY TRANSFER ASSOCIATED WITH MEAT TRANSFER 9 availability transfer associated with heat transfer may have to be modified to an approximation format 2) 20) = oft where T has been replaced by an average surface temperature T, al the solid physcal boundary where beat tanfer occurs. “The every ofa beat-transfer paces s determined by rmploying Bq, (3-5). Fora steady-state process without mass transfer or work intercon this equation reduces to 1g = % = > %, G2 That is, 1g is measured by the sum of the avaiabilty transfers in and out of the heat-transter region. Substitution of ki. (3-16) nto the above relation yields, for a supply reservoir at 7, and a sink reservoir at Tp, F)=nole-z,) 200 where Q is a postive value and Ty > Tp. Equation (3-21) is equally valid on @ rate basis. Equation (3-218) for fg has a graphical interpretation in terms of a 7S dite ‘gram. The heat quantity Q = ~Qx = Qs. For the intemlly reversible reservoirs ‘at T; and Tg the heat quantities are given by T4454 and Tp ASg. But TAS is a rectangular area on a T'S plot. The area representations of Q, and Qe are shown in Fig. 3-4. The areas under lines 1-2 and 3-4 must be equal in magnitude and Ihave '# common left border for convenicace in vomparing areas. The gray shaded ‘area beneath line 5-6 measures the imeversibility, since 1g — To(AS, + ASs). Note that the gray shaded area approaches zero in magnitude as Ty > Ts. Inthe preceding development the availabilty transfer associsted with heat transfer was restricted to a ixed and uniform boundary temperature or a sum of terms which aevount for different 7; values at various pats of the boundary. This terminology is especially appropriate for steady-state control-volume analysis. In many closed-system processes, however, the boundary teraperture is uniform but varies during the process. In this case the equations for ®2 listed above must be altored. In this new situation we begin with Eg. (3-14) in the form tase = (1-2) 40 om ‘and for a finite internally reversible process of a closed system with variable temperature set [Bho [en #P =W:- 0) Pav-Tas-S) G2)Advanced Thermodynamis for Engineers 92 svaiLasmiry aNALyss — Las FIGURE 34 Graphical representation of ireversibiity /g on 873 gram when best transfer Q occurs irom thecal reservoir A reserve B where 5@ has been replaced by (dU +P dV) and 8Q/T by dS. In this restricted cease @p may be evaluated in terms of property changes within the closed system Example 3-1. In Example 2-2 a heat transfer of 100 KJ occured between two ther- mal reservoirs with temperatures of 300 and 1000 K. For a Ty value of 300 K, determine che availability wansters and the imeversibilty of the heat exchange pro- cess, in kilojules, ‘Solution. "The availability wansfe is given by Bq, (3-18), namely, For the 1000 K reservoir un = ~10(1 223) = -r035 ‘The availabilty transfer to the 300 K reservoir is zero since Ty is 300 K. The lieversibilty ofthe process is given by Ea. (3-21).Advanced Thermals ’YAHLAMILITY TRANSFER ASSOCIATED WITH HEAT TRARSFER 93 to TF 7 [Note that the ireversbility oF loss in work potential equals the net transfer of| availabilty = soo0n( 3001100(555 - To00, = 708 ‘A simple but industrially important example of second-law efficiencies is in the use of energy from a high-temperature combustion source to provide ther- mal energy 10 processes occurring at lower temperatures. Process temperatures typically might range from barely above the ambient temperature 19 700-800 K. ‘Combustion source temperatures. might range from 100 to 2000 K. In general, a heat transfer Qs from the combustion source appears as either a useful process heat quantity Gor heat losses Q, to the environment. To simplify our analysis, we assume the source and use temperatures to be constant at 75 and 1, and any heat losses Q; occur at boundary temperatures T;. For a steady-state process the cnergy and availability balances for the closed system restricted to heat transfers across its boundary are 0=Gs-Oy- SG o-65(1-2 Ta (;-% rn) 20 ( ) Inthe development of an effectiveness for the beat-transfer process its useful to rearrange the availability balance so that the availability input is on the left-hand side of the equation, That is, 1) os( Fe)” el! or 05 bey boi +i + Do(1- Fei ‘This equation indicates thatthe availabitity ¢g.s carticd in by the heat transfer s appears eventually as availability transfers p,,, and Be ,, or is destroyed by inreversibilities £ within the system. Of the three products ofthe process. only one is useful, If the effectiveness is defined as useful product over required input, then ul = T/Tu) _ Pou 6a QI T/Ts) Pos ‘where both Qy- and Qs are taken to be positive, Each tem in this case represents the work obtainable from a reversible engine wiich receives heat Q at either Ts or Ty and rejecis heat at Ty. The above equation indicates that two factors control the effectiveness. First, the ratio Qu/Qs should be as close t0 unity as possi- ble (neat losses should be minimized). Second, the value of Ty; shoald approuch that of Ts. Since Ty is normally a required value ofthe end use, then 7s should beAdvanced Thermodynamis for Engineers 94 avauaumsry anatsis TABLE 31 ‘Summary of data for Example 3-2 Use TK dub) io ‘Aumospbers sink 300 0 m0 00 ‘Spice heating 313 42 68 Oa Proces steam generation 473 ne Firma opentien @ 367 3 cal Mase on @ = 1001, Ty = 1000 K, a Ty = 80K lowered, if possible. Ifa good match between Ts and Ty; is not possible, a poor effectiveness will result, The example below illustrates this point fora fixed valve of Ts and several possible Ty values required im industry. Example 3.2. In Example 3-1 a heat transfer of 100 kl occurs berween reservoirs oF 10U0 and 300 K and 7p = 300 K. For (a) the situation described above, and for (0) aduiuocal higher use temperatures of 4, 200, and 420°C, determine the effectiveness of the heat-ransfer process. Neglect heat losses. Solution. The secone:-law effectiveness in all these cases is based on Ea. (3-24), Pou _ Qull ~To/Ty) Fos” Qsd=T/Ts) ‘The availabilty of the heat supplied for all Ty values is ly 300 _ as = 04(1-B) = #2)= mu (a) Inthe original case Ty, = Ty. Therefore the availabilty supplied tothe reservoir at T) is 2210 and « = 0. All work capability of the energy has been lost (0) The sink temperatares of 40, 200, and 420°C might be chosen to represent, for ‘example, some operating temperatures commonly found in industrial practice, such 88 space heating, process steam generation, and furnace operat. The valves of Ty, by, sad ¢ for the four different temperatures are summarized in Table 3-1 ‘The results are not surprising: the lager the AT’ during heat transfer, the greater the value of Zg and the smaller the value of ¢, Thus the smaller the difference between the source and use temperatures, the more effective isthe use of thermal energy. 34 REVERSIBLE WORK, AVAILABILITY, AND IRREVERSIBILITY FOR A CLOSED SYSTEM ‘The general equations for actual and reversible work developed in Sec. 3-2 will now be applied to closed systems.Advanced Thermals [REVERSIBLE WORK, AVAILARILITY, AND RREVERSIULITY FOR A CLOSED system 95 34-1 Actual and Reversible Work for a Closed System A.closed system by definition is one for which mass flow across its boundaries is ‘excluded. Hence Eq. (3-5) reduces to ME + Po ~ TS) We AVA BS) _S°6,(1- PF} + toon (lows) 325) and in the format involving j thermal reservoirs Eq. (3-3) becomes Wage = 124 a Tes -Sai- (closed) (3-26) nd where £ = U +KE+ PE. On an extensive basis rather than on a rate basis, making use of Egs. (3-16) and (3-18), the above two equations become Hea = 16 1 Ay -25-S0,{i-B) stro = ME +PoV —ToS)—%o + Tore —_ (closed) (3.27) and Way = ME + VT) S05 I~ P}+ Tore ; ; = ME + PoV = ToS)- Po.) + Tome (Closed) (3-28) shore the direction of both Q, and Q, are measured relative to the elosed-system boundary. Both Eqs. (3-27) and (3-28) may be written on an intensive basis forthe setual useful work by replacing ', V, 8, and Q by e, es, and q. In addition, the Toor terms may be replaced by the ireversibility 1. Although only the heat transfer Q; appears explicitly in Eq, G-28). both equations above implicitly include any necessary heat transfer Qo with the environment at Ty. On either an extensive or intensive basis the reversible work is found by sesting cm = Gus = 0. That Wary = AE+P)AV—ToAS Bg (closed) 2 and Wrorw = AE +PrAV-ToAS Bon (closed) 30) ‘where the last equation has been written fora single reservoir at Tr. Now, consider 8 stationary closed system undergoing a process where no reservoirs at 7} are present. The specific useful work transfer fora provess between two end states 1 and 2, while exchanging heat solely with the environment and under reversible ‘conditions. is given by Wrevan = (ua ~ ui) + Pyles ~ 01) ~ Tosa 81) (closed, ge = 0) B31) Under these restrictive conditions the only data required are u. p, and s at the ced states and the environmental pressure and temperature,