Engineering Thermodynamics FOURTH EDITION Burghardt HarperCollinsCollegePublishersConversion Factors Area(a) TR = 0.0929 mt in? 698.18 mm Densiy ip), Tb? = 16018 kg/m? oug/R? = 515.379 kg/m nergy (E,W, U,PE. KE. Q, 9) Tit 118 51 [i ~ 798.169 Foe LtTeal= 4.18687 Bawwpy (5) Tita /R — 1.899260/K oreo (F) Tibi 44882 N dye = 110-9 Heat (Q) see Energy Heat fw este (@) 1 Bts/h= 02931 W tue 1.0551 KW Heat taser cveticiet (i) Btu eo = $478 W/oK Length (2) T= 02088 m Lin = 2340 im=i837in [m= 1.6003 km = $280 f Mass) 0254 {Shor ton = 2000 tom Power) Biu/h=0.2931 W 1 Bs = 10881 AW thp= 745.7 W hp = $80 tas 1 hp = 2548.5 Buu/he TkWe 1341 hp Pressure) bar = 100 KPa Tin, He 04912 psi min He = 0.1333 kPa {atm = 101325 KPa 14.696 psa {atm = 760/mm Hg = 2092 in. He Specie enory (gm 2h x pes Ke.) ‘Bta/Tom = 23361 1) ka Specie entropy (0) Bylo = 41868 KS hg 1 uo = 778,169 fo ‘Specie heat 6.) Se Specie entropy Specie volume (3) TR? tom = 0.062 428 mig Specific work (wee Specific enrey “Temperature (7) TI) = L8 TUK) TIC] = 5/9 (1F) -32) TE]= 9/5 TIC +32 TIC) = TIK}~ 27315 TIF} ~ TIR]— 459.67 “Thermal conductivity (2) Uta heteP = 1.731 Wark “Thermal duis (a) TRE /sce~ 0.0829 m/s Ise = 288) X10 ys Velocity) y/o 0.3048 m/s [mph = 04203 m/s Viscosity, dyramie (0) 1 Tonia = 1488 Neji? { centipoise = 0.001 Nise Viscosity, kinematic () Race 0.08029 ms ERS/hr= 2.581 % 10-7 m/s Volume V) Tin = 353147 8? = 1000 ters TUS. gal 3.7853 bie [R= 7461 US. eat 1S. bare = 42 a Work (se Ener Constants Acceleration of gravity a sea lev 32.1739 fuse! = 907 m/s Avogadro's number TU kemol = 6.023 X 10 molecules, Stefar-Rolezmana oastant(¢) S67 1-* Wym=K* = 0.1914 X 10-* Bray Re ‘Universal gas constant (&) 3145 Akama K= 1545.32 ebm RTo Linda and Phyllis ‘Sponsoring Eator: Joho Lenchek Project Paiter: Ronee Wire/CarolZombo Art Director: Julie Anerson (Gover Desig: Julie Anderson (Corer Mlustration: Rolin Graphics Prodition Administrator: Bran Bransteter Composter: Prosesive Typoprapher, le. Printer and Binder R. R. Donneley & Sons Company ‘Cover Printer: Th Lehigh Press, ln. Engineering Thermodynamics, Foweh Edition Copyright© 1993 by HarperCollins College Publishers Allghts reserved. Pinte inthe United State of America No part ofthis book maybe used ‘or reproduced in any manner whatsoever without writen permission, except inthe case of trie quottions embodied in eriealartices and reviews. For information address Harpe. Collins College Publishers, 10 East Sind Street, New York, NY 10022, Library of Congress Catalogng-ia-Publication Data Burghardt, M. David, Engineering thermodynamics. —ath ed/M. David Burghardt, James A. Harbaeh, bem, Re. ed. of: Engineering thermodynamics with applications, 3rd ed. ©1986, Includes index ISBN 0.06.081049.3 1. Thermodynamics. I. Harbach, James A. 11, Burghardt, M. David Engineering thermodynamics with applications, Il Title Tu6s887 1992 621.402"1 4020 9230663 cP: m3 8 95 8876548 Contents preface Chapter 1_ Introduction Chapter 2_ Definitions and Units 1s 2.4 Macroscopic and Microscopic 29 Pressure 37 Bralysis 18 2140 Equality of Temperature 35 22 Substances 16 241 2eroth Law of 213 Systems—Fined Mass and Fixed Thermodynamics 35 Space 76 2.42 Temperature Scales 36 2.4 Properties, Intensive and 2.13 Guidelines for Termodinamic Extensive 19, Prabier Solution 39 2.5 Phases ofa Substance 20 Concept Questions 41 26 Processes and Cycles 20 Problems (si) 21 27 Unit Systems 27 Problems (English Units) 45 28 Specie Volume 30 Computer robiems 37 Chapter 3_ Conservation of Mass and Energy 4s 3.1 Conservation of Mass. 49 3.6 Further Examples of Eneray 322 Energy Forms 5? saalyis 23. 33 Frat CorlyoftheFiestiaw 70 Concept Questions 88 3.8 Energy a8 a Property 74 brbiems ()) 90 3:5 secon Corallny athe Fst Problems (Engish Units) 96 law 75 Computer Problems. 700 Chapter 4 Properties of Pure Substances 441 The State Principle 102 {47 Thvee-Dimensonal Surface 107 42 LigudVapor Equlirium 70348 Tablas of Thetmodynamic 4.3 Saturated Properties 103 Properties 109, 4.4 Critical Properties 106 Concept Questions 120 48 Solid guid Vapor Problems (51) 121 Equltrium 305 rablems (EngHsh Units) 125 46 Quality 107 Computer Problems. 128Chapter IdealandActualGases 128 5:1 IdealGae Equation ofstote 1295S Gas Tables 108 5.2 Nonidealcas Equations of Concept Questions 156 State 122 Problems (8) 154 5.3 Specfceat_140 Problems (nglth Units) 957 514 Kinetic Theory Pressure and Computer Probes 158 SpociflcHeat ofan ideal Gos 145 Chapter 6 Energy Analysis of Open and Closed Syst __ Systems 160 {6.1 Equilbvium and Noneauium 66 Transient Flow 787 Processes 160 Concept Questions 194 62 Chsea Systems 182 Problems (S19 63 Open Systems 168 Problems (English Units) 201 6.4 Poiytopic Process. 179 Computer Problems 205 65 ThreeProcess Cycles 185 Chapter 7 The Second Law of Thermodynamics and the Carnot Cycle 207 774 inwoduetion and Overview 208 7.8 Second Corolaty ofthe Second 722 The Second taw of law 226 Thermasimamies 208 119 Thermesynamic Temperature 17.3 The Second taw for Cycle 240 Seale 226 TA Carnot Cycle 212 Concept Questions 229 755 Mes Efectve Presse 276 roblens (3) 228 78 Reverses Camot Engine 223 robles (English Units)_233 2727 Frat Corry of the Second Computer Probiems 235 aw 225 Chapter 8 Entropy Eiazsc 6.1 Clos equality 257 9. Heat and Work as Areos 257 8.2 Derivation of Entropy 239 18.40 The Second Low for Open 8.3 Cslulation of entropy Change Systems 258 forieal Gases 24 8.41 Third Law of 10.4 Relative Presute and Relative Thermodynamics 262 Specie Voime 245 18.12 Further Considerations 262 8.5 Eriropy of aPure Substance 248 Concept Questions 264 8.6 Further Discusion ofthe Second Problems (5) 265 {aw for Closed ystems 257 Drobiems (English Units) 270 8.7 Equilbum state 255 Computer Problems 274 8.8 Carnot Cyele Using FS Ceorsinstes 256 Chapter 9_ Availability Analysis = 25 ‘511 inrodvction 275 9.3 Flow avalabiny 287 5.2 Availity Analysis for Closed 9.4 Second-Law ficiency. 293 Systems. 277, 9.5 Avallable Energy —A Special Problems (Sl) 305 Case of Avalabity 258 Problems (English Units) 310 Concept Question’ 50 Computer Prabiems 314 Chapter 10_ Thermodynamic Relationships 315 10.1 interpreting Diferential ané 10.7 important Physical PartalDervatves 316 Coefieients "337 402 Animportant Relationship 318 10.8 Reduced coordinates for Van 103 Applzation of Mathematica Der Waals Equation of ‘Methods t9Thermasynamie state 333 Relations 220 Concept Questions 337 10.4 Marwel's Relations 922 Problems (S337 105 Specie Heats, Enthalpy and ‘Problems (English Units) 339 incenal Energy 322 Computer rebioms 340 106 Clapeyron Equation 327 Chapter 11. Nonreacting Ideal-Gas and Gas-Vapor Mixture 111 WdeakGas Mintres 342 ‘Problems (st) 354 11.2 GasVapor Mixtures 353 Problems (English Units) 367 1153 Psyemometer 367 Computer Froblems 370 Concept Questans 366 Chapter 12_ Reactive Systems 371 12.1 Hydrocarbon Foals 272 12.10 Secondiiaw Analysis 398 122 Combustion Process 372 42.11 Chemical Equiorum an 123 Theoretical air 374 Dissecition 406 124 Air/Fuel Ratio. 375 122 Steam Generator 1255 Products of Combustion 393 ficiency” 416 4126 Enthalpy of Formation 38 12.413 Fuel Cele 476 127 First Law Analyse fr Steno Concept Questions 42 State Reacting Systems 387 Problems (Si) 421 128 adiabatic Fame Problems (English Units) 427 Temperature 390 Computer Problems 30 128 enthalpy of Combustion, Heating Value 396 Chapter 13_ Internal Combustion Engines 432 13.4 Introduction 432 13.7 Wankel Engine 465 132 Ale Standard Cycles 423 13.8 kagine Eficiencies 465 133 Actual Diesel and Ona 13,9 Power Measurement 468 Cycles 453 Concept Questions 474 13.4 cle Comparisons 485 Problems (SI) 475 135 Engine Pertormance Probtems (English Units) 420 fnaijis 436 Compare Pobiems 22 13.6 Engine Performance Analysis 464 ee ———_______—a 483 Chapter 14__ Gas Turbine: 142 Funcsmentl Gos Tine 187 Reheatng and Gye 483 Intercecing 507 142 ele Anas a4 140 Aiea Gos Tunes 512 13 Efiionies 387 Concent Questions 519 484 Opencyce Anais 404 Problems (5) 520 145 Combustion Eiceney 498 Droblems(Enlh nits) 525 186 Regenerston #58 Computer Poses 527 Chapter 15 Vapor Power Systems —__ 529 154. Vapor Power Pants 530 15:10 Bottoning Cys ond 15.2 Toecomnat cycle 537 Cogeneration 565 153 Thelaea Rankine Gcle_532 15.11 Comtined Gas Vapor Power 18a Factors Conttbuting to Cycle Gyeles 575 reverses and 45.12 Steam Tene Aehoat Factor leses 538 andcondion Gave 578 15:5 Improving Rankine Cycle 15:3 Geothoal Enea) eS Tieng saa 18.14 Second ins Analysis of Vapor 15.6 The lal Rankine Reheat Power Cycles 583 Gee 545 15.5 Actual Heat Slonce 15.7. The lea Regenerative Considerations 586 Rankine cycle 50 Concept Questions 520 15.8. Reheat Regenerative problems (5) 589 Gye 59 Froblems (nglsh Units) $97 159° ny Vapor Cyeles 565 Computer Preems 603 Chapter 16 Refrigeration and Air Conditioning Sefeoee x clei eens ‘ee Siac pe conpeson abs att aaa casei | Chapter 17 Fluid Flow in Nozzles and Turbomachinery 676 47.1 Consewvotionof Mess 677 47.42 Fow Measurement 732 172. Conservation of 17:33 Wina Power 713, omentum 677 1748 Energy Transfer na 17.3. Acoustic Velocity 620 Turbomechine 716 17.4 Stagnation Properties 682 17.15 Flug Rotor Energy 175 MachNumber 683 Teansfer 724 176 Fist Law Analysis 625 Concept Questions 735 12.7 nozdles 696 Froblems (31) 736 178 Supersaturation 696 Problems (Enash Unis) 739 178. bifuser 700 Computer Prebiems 242 17.40 Shock Waves. 703 $7.41 Flow Aeros a Normal Shock 708 Chapter 18 Heat Transfer and Heat Exchangers 73 38.1 Modes of feat Transfer 74418. Crtcl Insulation 182 Laws of heat Tanstr | 748 Trieness 758 183 Combines Modes of Meat 18.7 Heat Exchangers. 759 anster_ 759 Concept Questions 772 18.4 Conduction through 3 Broblems (S773 Composite Wall 753 Problems (Engh Unis) 776 185 Conduction in Cylincicl Computer Problems 777 Coordinates "753 References ns List of Symbols 780 Appendix Tables yas ‘AX Gos Constants an Specie ‘AS. Sotwated Ammonia Table Heats at Low Pressures and {Siunis) 200 wecgrr) 705 10 Superhested ammonia Table AZ Properties of Aira Lowe (Glunits) 202 Pressures (S1Unis) 786 [AA Saturated Refrigerant 12 Table AB Products—400% Theoretical (SiUnis) 204 Airmat iow Pressures 789 ANZ Supetheated Refigerant 12 AG Products 200% Theoretical Teble(Stunes) 608 ‘iret tow Pressures 750 —-AAB Properties of Alt tow AS. Saturated Steam Temperature Presses Ealish Unis) 610 “able (1 Unis) 792 ‘An4 Saturated Steem Tenperature AG Saturated Steam Pressure Table Table English Units) #2 (stunts) 753 [AAS soturatea Steam Presse Table AT. Supetheated Steam Vapor Table EEnaish Unie) G39 (stunts) 736 ‘A.6 Scpmeated Steam Vapor Table AB Compresed Liu Table ‘Eratsn Uns) 876 {siunits) 758ALT Compressed Loud Teble (Engen Units) 279 ‘A. Saturated Ammonia Table (Engish Units) 620 1.19 Supethestes smmonie Table (Enolsh Unis) 27 18.20 Saturated Refrgerent 12 Table (Engish Units) 827 A.21 Supemeoted Reltigerant 12 Table (English Units) 29, |A.2 Properties of Selected Matera at20°C (68°F) 833 'A.23 Physical Properties of Selected Files 234 8.1 Mole rthalpy-Entrops) Diagram for Steam 836 8.2. Temperature Entropy Diagram {or Steam (S\Units) 838 8.3(a) Ammonia-WaterEqulibrium Chart (5 Units) 232 18.3(b) Armonia Water Equilibrium Char (English Units) 40 B.a(a) Psychrometic Chart, (SiUnit) 847 1B.a(b) Psyehtometic Chart English ca cy ca Answers to Selected Problems Index nits) 842 Enthapies of Formation, Git Funetion of Formation. snd [Absolute Entopy at 25°C and atm Pressure 843 deal Ga Entralpy and [Absolute Entopy at atm Bressre 43 Enthalpy of Combustion (eating Valu) of Various Compounds. 854 Natural Logarithm of fquiltrivm Constant K 855 Solving Thermodynamics Probiems with the Personal Computer 855 863 an L Preface ‘This text presents a comprehensive and comprehensible treatment of engineering thermodynamics, from its theoretical foundations to its applications in realistic situations, The thermodynamics presented will prepae students fr later courses in fluid mechanics and heat transfer In addition, practicing engineers will find the applications helpful to them i their professional work, The textis appropriate ran introductory undergraduate course in thermodynamics ad fora subsequent course {in thermodynamic applications. Many features of the text distinguish it ffom other texts and from previous ceditions ofthis text, They include ‘A systematic approgch to problem solving + Am instructor’ solutions manual that includes saltions to all problems and ‘that uses the same systematic approach found in the examples ‘+ Over 1500 problems in SI and English units, 90 requiring computer solution, plus 130 solved examples ‘ Chapter abjectves highlighted at the start of each chapter + Expanded and amplified development of the second law of thermodynamics, stressing avalahilty analysis; * The integration of the use of the personal computer for solving thermody. namics problems based on the use of TK Solser® and spreadsheet software; ‘The inclusion ofa sk of TK Solver® files that can be used as provided, oF ‘modified and merged into mode's developed to analyze new problems, We believe that this text breaks new ground in the presentation of thermody- namics to undergraduate enginccring students, Te iatepatin ol ie use of TH Solver® and spreadsheet software isoneimportantaspectafthisadvance Inadition toineluding files fo determining properties of steam, refigeramt 12, andar, the diska supplied with the text includes model for analyzing many thermodynamic processes land cycles Unlike most other available software, these TK Solver® models can be teasly modified to analyze new problems. This provides the student with a powerful set of tools for applications in later design courses and in their professional careers AS {an indication ofthe software's power, although it is2 long tal-and-error process to {determine the percentage and effect of only one product's dissociation ina combus tion process, one of the TK Solver® models supplied can analyze combustion reac: tions with up to three simultaneous dissociation reactions, Wale we believe that the integration ofthe computer solutions enhances the thermodynamics course, the text fs also writen to be used without the software “Another key feature hat elevates the text isthe expanded discussion and analysis of thermodynamic fundamentals and applications, An underlying there ofthe text is that understanding enerey and energy utilization is vital tothe well-being of an industrialized society. Ths i underscored when alternative energy sources such as solar, geothermal, and wind ae discussed. Furthermore, the environmental effects of acid rain and global warming are discussed inthe chapter on reactive systems. ‘Annes feature ofthe text sa systematic problem solution methodology that is adhered to in the fext and the instructor's solutions manual. This methodology puides students into thinking about the problem before proceeding with its solution, Itencourages students o approach the problems logically to state assumptions used, to detail the step-by-step analysis, to explicitly include units and conversions when ‘numerical valuesare substituted, and o note inconclusion key points inthe solution, ‘We encourage faculty 19 require theirstudentsto follow tis format in ther problem solutions The end-of-chapier problems range in complexity from those ilustrating basic ‘concepts to more challenging ones involving judgment onthe part of the student. In the applications chapters, open-ended probiems allow the students to investigate alternative solutions. The provided sofware allows students to model complex sy- fems, vary parameters, and undertake parameter variation in seeking optimum solution, Inthe chapter on reftgeration and air conditioning, the R 12 property ‘models and the psichrometric chart models allow solution of sophisticated HVAC problems. Second-law analysis is ever more important in an era of heightened energy awareness and energy conservation. A thorough development ofthe second law of thermodynamics is provided in Chapters 7-9. The concept of entropy prociution is ‘developed in Chapter 8 and used throughout the application chapters, as are the svailaility concepts developed in Chapter 9. The ramifications of the second law receive thorough discussion; the student not only performs calculations but under stands the implications ofthe calculated results ‘We would lke to extend our gratitude to the following reviewers, who offered valuable suggestions forthe fourth edition: Lynn Bellamy, Arizona State University: ‘Alan J. Brainard, University of Pittsburgh; F-E. Brooks, University of Saskatchewan: James Bug, University of Saskatchewan; Clinton R. Carpenter, Mohawk Valley ‘Community College; Donist Fairchild, Rogor Wiliame College: Waller R. Ka ‘minshi, Central Washington University: B.L Leidy, University of Pinsburgh; Robert 'A. Medrow, University of Missouri — Rolla; Edwin Peiack, University ofthe Pacific: vrerace xl ui, Stndr, outers Cleo Teco cog Sh SinieComm ny College EM Spurow, Univesity ofStinnasur mon Ton Ceoce lene Int of Tent Richa NC. Wace lao Sat Cote nae Coxon Sout OatoaStac Univents evra armen OTs rtisestnnes nd sppsio on opromeg oe eee ae Tiscuope tha he tex mess oar ein caghesing al bes weld tiene Behe ete David Bupa wh HaresIntroduction ‘Thermodynamics is the science that is devoted to understanding energy in all its forms, such &s mechanical, electrical, chemical, and how energy changes forms, ¢ the transformation of hemical energy into thermal energy, for instance. Termody amies is denwved from the Greek words therme, meaning heat, and dams, mean ing strength, particularly applied to motion. Literally, thermodynamics mesas “heat strength," implying such things as the heat liberated by the buraing of wood, coal, ot oil IFthe word energy is substituted for heat, one can come to grips with the meaning And scope of thermodynamics. It the science that dels with energy transforms: tions: the conversion of heat into work, or of chemical energy into electrical enery. ‘The power of thermodynamics lies in its ability to he used to analyze 2 wide range of energy systems using only a few tenets, to primary anes being the First and Second Laws of Thermodynamics. Thermodynamics applies very simple yet encompassing laws to a wide range of energy sysiems that have major import in our sacict, for ‘example, energy use in agriculture, electric power generation, and transportation systems, ‘We will examine the following energy conversion systems in more detail * A seam power plant, fundamental to he generation of eectie power, + Auvinen coubustion engine, sred by many of ws daily in our automobiles * Direct energy conversion, particularly photovoltaic conversion of sunlight into electricity, «projected major source of electrical power2 cinoreR 1 sivrRooucriON ae ens oO] : gure 1.4 A simplifies vapor power ec ‘* Cogeneration facilities where power is produced and what had formerly been ‘waste hea is used for heating or cooling. ‘+ Our current energy consumption patterns, and energy conservation policies ‘that industrialized! societies may follow in the future withthe resultant chal- lenges for engineers The Steam Power Plant “The first aw of thermodynamics states that energy is conserved: it can change form, ‘but it cannot he deste. This very simple, fundamental statement allows us 10 investigate the behavior of many devices and systems (combinations of devices). One ofthese ithe steam power plant, an energy system that i essential tothe industil- ied world, sit often is use forthe generation of electric power. Figure |.1depictsa simplified steam power plant. Fuel is burned to release heat ina steam generator, similarin concept tothe il-or gas-fired boilers used to providesteam or hot water for beating in homes. The process transforms the fue's chemical energy ta the thermal ‘eneray of combustion gases, The heats used to boil water under pressure in thesteam tenerator (boiler. The steam leaves the generator and passes through superheater Tubes, where mare heat is added tothe steam it then passes through the turbine, ‘where itinereasesin volume, decreasesin pressure, and performs Work Ds CaUSINg turbine rotor to rotate. The turbine is coupled to a generator, which i used to generate electric power. Thus, in the turbine anather process transforms some ofthe HAPTER 1 /TROBUCTION 3 Figure 12 A reciprocating itera combustion engine thermal eneray of the steam into mechanical work, The steam is then condensed, Tiguefied, and pumped back tothe steam generator. The second law of thermody ‘namics tells us how much thermal energy can be converied into Work, Not al of it can be, ‘To fully understand a steam power plant requires knowledge of substance prop ‘erties: why water behaves a it does, why combustion occurs, what ae the combus- tion prociuts, what isthe mechanism of energy transformation. Thermodynamics allows us to determine these properties, experimentally and theoretical Internal Combustion Engines Another standard power plant that many of us use everyday isthe internal cormbus tion nine used to power automobiles and many ather machines (Figure (2) The1 | “lo ee oe is a Figure 1.2 Transformation of fl enery int vehicle motion, engine may be viewed asa smal powerplant: ful ishurned, and the energy from the ‘burning fuel is transferred to the pistons, whose gears turn the wheels, thus moving theautomobile, The transformation ofthe fuels chemical energy into vehicle motion isshown in Figure 1.3. In these times of eneray scarcity, we need to develop an understanding of the transformation process so we can minimize inherent losses of energy quality. Ther rmodynamic analysis seeks to determine ahead of time how much work we may ‘expect ftom an engine and, through experiments, how efficent the engine is pet- forming. This is very important in minimizing the pollution from exhaust gases, A typical engine's exhaust contains unburned hydrocarbons, carbon monoxide, carbon lide, and nitric oxides, all of which decrease ar quality, We need to minimize the ‘otal pollution, eliminating those types that are mvost harmful ‘The gas turbine is another combustion engine, typically used on jt planes and forsuppiementaleleciric power generation. Airis compressed and energy added tit bby burning ful in @ combustion chamber: this mixture —the products of combus- tion, ar, and bursed fuel —expands through a turbine, doing work, which drives the compressor and electric generator (Figure 1.4). On a jet engine, the work of the Figure 14 A gnscurbine unit coworen 1 /mmooucron 5 Figure 15 The hynogea-oxjs fuel cl turbine is used ony o drive the compressor, anc the exhaust gases rom the turbine, lundera higher presure than the outside aie, expan through a nozzle, increasing in Velocity This increase in velocity generates 8 propulsive force an the engine and on the airplane to which itis attached. All these analyses have a common purpose, 10 consider haw efficiently the chemical energy ofthe fuel is converted into mechanical energy and wits thisknowl- ‘edge to search for ways to improve the conversion process, The prooesses of eanvert- ing energy are diferent depending on the mechanical structure (autoniotive engine ‘versus steam powerplant), but the laws of thermodyamies governing enersy com version remain the same, Direct Energy Conversion Some energy converters do not rely on intermediate devices 10 produce work — electric poser in thiscase. Two familia direct energy coversion devicerare Nel cells in which chemical energy is converted directly to eletrcal enerpy, ad phorovaliie cals in which the sun's radiant energy is converted directly to electrical energy Figure [5 illustrates a simplified fuel cell using hydrogen and oxygen. The hydrogen is oxidized atthe anode, giving upto electrons, andthe oxygen is reduced atthe cathode, receiving two electtons. The load is connected tothe two poles. “The half-cell rections are Hyg? 2H*+2e” = 0.0 vos P= 1.23 volts gy + DHT + 20° H,0 0h “Thus the voltage ofthe cell has 1.23 volts, nd ifthe load resistance is known, the current foing through the load may be determined with Uns fv One ofthe most promising renewable energy forms is photovoltaics, the direct, conversion of sunlight into electricity. Current laboratory madels can attain acon6 Ccaaeren + wTRODUCTION Baie ese ee 7 Figure 1.6 Charge distribution ina PN nove oe photovoltaic call oo ° version efficiency of 254% on small cells and an average efficiency of (3% for fellsa square foot in area. Production costs are dropping, making the units more economical How does this conversion occur? Photovoltaic cells area type of semiconductor involving a PAN junction, At a P-N junction is a voltage potential created by positive-hole P-layer, which contains movable positive charges or "holes." and a ‘negative N-layer, which contains movable negative electrons. When light with suf- cient energy enters the crystal, elecvons are released from ther atornic bonds and ‘migrate to an electrode. A wire connected from the negative electrode 1 a lad leads back tothe positive electrode, where the electrons combine with the positive hoes. A barrier atthe P-N junction prevents the electrons from instantly combining with the hoes in the P-layer, Forcing them instead to flow fram the electrade through the load to the opposite electrode, No material is consumed, and the cll would theoretically last forever, excent for radiation damage which limits the working life of the cell Figure i. illustrates a P-N paotovoltaic cell. The barrier layer prevents diffusion ofolesor electrons fom the Player tothe Nelayer, or vce versa The crystal absorbs Sunlight, producing an electron and a hole. Ordinarily these would immediately recombine, and the effet of he light absorption would bean increase in crystalline temperature, However, because of the potential barrier at the P-N junetion, the electrons migrate to one electrode andthe hols tothe other. This produces paten- tial diffrence, and a current car flow berveen the electrodes when a wire connects them, Very important tothe successful operation ofthe cell are controlled doping With selected impurities and the absence of other impurities. The effec of other impurities isto allow recombination of holes and electrons, rather than a fow of curent. Because of engineering advances in refining and doping, photovoltaics is ‘Row a practical means of smallscale power generation. Cogeneration Another type of energy system of growing importance is a cogeneration system. (Cogeneration means using the same energy source for more than one purpose, such Our Energy Consump! ouneneR + pergapucnon 7 ie 198 gure 17 Comparison of neg sources in 1973 nd 1988 in he Utd asusing the waste heat from an engine forspace heating. Cogeneration facilities often generate electricity locally, such asa university using is own diesel-electric genera- tors. The waste hea rom the engine used for additional purposes, perhaps or space heating or for air conditioning, asodd a that sounds, There are large airconditioning systems that use heat 2s the energy source: these are called absorption refrigeration systems, So, rather than having an engine that is 40 eficient in generating eectric- ity withthe waste heat from the cooling waterand theexhaust being disipated tothe alroosphere, a cogeneration facility uses this waste heat for other purposes, This increases the overall eficency ofthe unit and decreases the total fuel or utility costs thatthe university’ has to pa n Lifestyle ‘Many studies! indicate thatthe world will have greatly diminished petroleum and ‘mineral resources in the near future resources that sustain the stand of living the industrialized world enjoys. All aspects of manufacture and living must become more energy efficient a the cost and scarcity of resources increase, A knowledge of thermodynamics isthe fst step. It allows engineers to create new systems and devices that will reduce our energy consumption and improve our energy utilization, "How did we get in this predicament in the frst place? We love energy. Our lifestyle and our standard of living depend on a very high rate of consumption of energy. We have forgotten that all the electricity and gasoline come from a finite supply of fossil fuels. Because it isa finite supply, twllbe depleted very soon, perhaps ‘within our lifetime for domestic oil and gas reserves, Figure 1,7 graphs the sources of energy that fuel our lives. The largest source is petroleum products —gasoline and fue ot —that we use in our cars, homes, and power plants. Notice the diferenes in the amount imported in 1988 versus 1973, the time of the OPEC oil embargo, The United States will become more sensitive to variations in petroleum supplies 2s it produces les ofits total consumption, because other enerey forms do not perform pettoleum’s function in society, for example, providing fuel for ears. Our total energyCoutereR + nTRODUCTION ‘gure 1. Change in US. energy sources consumption hasbeen supplemented by increasesin coal and nuclear power progus- tion, Figure 1.7 does not indicate where the fuel reserves ae. The United Staves has a Jargecoal supply, but the domestic petroleum and natural gassuppliesare decreasing, ‘making imporss more imparant. Various factors are weighed to estimate when the {domestic supplies will be depleted and when the United States wil become totally ‘dependent on foreign supplies. Certainly in the next ten to twentyfive Years the United States will be nearing this situation. Economic and political problems will result ftom this inreasing dependeney. The problems are economic in thatthe cost of fuel will ise dramatically, causing inflation and social pressure, and potitcal in that other countries wil be vying for the same energy’ sources. [Engineers mast be very aware of the social and politcal pressures associated with technical changes they design. Figuee 1.8 represents a forecast of the changing pro- portions of the energy’ sources in the United States forthe next forty years. I is apparent that oiland gaswill decrease significantly and that coal willbe the remaining Tossl fuel, with mucleay solar, and hydroelectric Being Une other energy sources. “The United States has large coal reserves that can be used for power generation, «coal gisifcaton projects and coal liquefaction processes. Studies have indicated that ‘theres suicient coal to provide far ourenergy need forthe next fous hundred years, However there are tremendous environmental problems associated with expanding the use of coal, Much of tae coal that is accessible is strip-mined, a technology that arouses environmental roup action and requires water tat isneeded for agriculture and drinking supplies in the same geographic resions. In addition burning cosl involves ar pollution and sir quality issues. Coal with a high sulfur content must be processed 40 remove as much sulfur 2s possible because ofthe direct correlation cearten 1 /wrioouerion 9 between sulfur and acd raf, Nationally 20% of the coal reserves have a high sulfur ‘content, with the fluure at 43% in coal regions east of the Mississippi River. The ‘combustion of any hydrocarbon fuel producescarbon dioxide, heightening the prob- ability of global warming Nuclear power plant construction is at @ standstill in the U'S, forthe legal impediments to building 2 plant are virally insurmountable, However, nuclear power produces about 15% of US, electric power. In France, over Us ofthe electric powers produced at nuclear plans. Nuclear plans create significan: waste disposal problems one ofthe key aeas of concern Internationally, however, nuclear plants are being constructed as an alternative power source, and the United States may se them appear agai if the time and cost for construction can be decrease ‘Renewable energy supplis, solar and hydro, hold some promise for future de velopment, panicularly small-scale solar power. Hydroelectric power has severe jeavironmental impacts associated withit, Dams must becreatd, land flood), ater tables changed, and the habitat for certain species destroyed, All these steps are possible, but the process takes time and is sure 10 engender significant opposition. Certain types of solar energy utilization, paricuarly passive solar enersy for home heating and photovoltaics fr electric power generation, are increasingly being used, During the industrial age, energy—fucl—has replaced people and animals in performing work in manufacturing, agriculture, and transportation in all areas of ‘commerce and industry. Figure 1.9 graphs he change ofenergy source for work Ver gue 1.9 Source afenery used for workin the United States, Sonree'C. A. ‘SHALL. - Cleveland. and R: Kaufinann, Prergyand Rewarce Qual The Ecology othe Padus Prces, New Vox. John Wile) and Sons 1486)‘ovnerer + fiwrgooucnon x Figure 1.10 Eneray wsage apd worker productivity. Soli fine is energy use dled ines labor product. Both mensureare indexes, 1967 ~ 1.0. Source J. Clevelaad RCostanca, © A: 8. Hal, Kaufiaan, “Energy and he U.S Econom: A Biophysical Perspective," Science [1984] 235380097 Copyright 1988 AAAS) time. People use machines (energy provided by fue!) for manufacturing jabs, be ita riveter ora computer assembler. Figure |, 10 illustrates the increase of productivity associated with this increased energy utilization Te beginnings of thermadiynamics in the nineteenth century coincide with the ssc in energy consumption. As we reach a tecminus in the nonrenewable Fuel sup- plies, we must search for productivity gains om mean ole than energy, Engine ingcreativityiscertainly needed. Figur 1 ilustratesthe near LOO? dependence on rnonrenewable energy sources in the United States Using foreign supplies to replace ‘domestic sources is no long-term Solution either, a al fossil fuel supplies are finite Immediate aevions can be taken to improve energy wtlzation and conservation Because fuel costs have boen very low, the manufacture of produets has tended toward lowest initial cost. Operating costs were largely ignored. For instance, itis possible using curent technology 10 build domestic refrigerators that use a maxi- ‘mum of 700 kilowatt-hours (kw) per year rather than the mximam of 1800 kwh allowed ia eusteut nes, California passed a law requiring that by 1993 all refiger- ‘ators achieve the greater efficiency. Engineers created models with design changes requiring more insulation and more effiien: compressors, motors, condensers, and CoUBTER 1 /WTRODUCTON 41 Figure 1.11 USS ue consomption, percentage of noneenewable fl evaporators, These changes cost only $50 more per unit. Superficient models ere being constructed that annually consume 100 kwh, St ofthe 1900 kwh units Switching to natural and fluorescent lights from the predominant incandescent Hight bulb will save equaly large amounts of electricity. A 75.W incandescent light bulb hasan average lifetime of 780 hoursand produces | [80 lumensof illumination; 4 20-vatt fluorescent light has a 7500-hourlifeand produces |250 lumens of ilu nation. Ninety percent or more of the incandescent bullsenergy isdisspated ashest, A flow of electricity heas the bull’ filament to high temperature, making tke filament glow and produce light. Ofcourse, this heat must be removed by abulding's air-conditioning system in hot weather. Fluorescent bults are coated with phosphor powders that glow when excited by ultraviolet light. The ultraviolet igh isereatedby fonizinga gas within the tube nthe early 1970s automobiles had a comparatively low Ae: average mileage, 15~16 miles per gallon (mpg). Since the energy criss in 1973 the feet average has ‘sen to 25-26 mpg. This represents tremendous savings in fuel when you consider the numberof cas on the road and the miles driven, Some automobiles curently obtain $0 mpg or better, By decreasing vehicle size and weight and by using new materials, more efficient engines, and hetter aerodynamic desig, the feet averaae can continue to rise, Not only will personal transportation systerns change with eereased fuel availability and/or significantly higher fuel costs, buc other systems willchange:e wall, Over thepazt forty years uilroadtianspuntaion of pao as Beeh replaced by trucks. The days forthe mass transportof goo via trucks are numbered. hhowever, because for long-distance hauling tains are at lest five times more fuel2 Cchaeter 1 /wwraooucTiON efficient shan tucks. Compace a feight train to the numberof trucks that would be rede to haul the same goods, ‘Populations and societies prosper because of abundant food and energy supplies Part of te reason the United States has been abe to suppor its standard of living at the present level is that it exports agricultural products, creating a trade surplus to partially counter the trade deficit in eneray. Problems lurk inthis vital sector ofthe fvonoms. Farming has developed into a highly energy-intensive operation. Farms have become larger as a result of this. Agricultural engineers need to create new technologies and methodologies to suppor this vital economic sector. The tractors needed for tilling the soil are not the prablem, although techniques in plowing eer bars! hasa mass of 20tbm and. volume ofS gal ess density is 62.4 hm Determine te fotal mass and weight of the hartl when cis filled wth beer. 2.0 A tank's pressure gage indicates thatthe pressure inthe tanks 80 psig and the atmos hero pressure is 2.72 in. Hy Determine the tanks absolute presse "211 A unk has a vacuum ange attached o itindicating 28, Hg (vacuum) whese atmos phere pressure is 14.3 psa Determine the absolute pressure in the tank {A tonk has a vacuom sie attached to it indistng 28.6 in. Hi (vacuom) where umospherie peste i 9.8. Mp absolute, Determine the absolute gessue in the tank A trometer canbe used to mcasurean airplane's altude ty comparing the barometsc presureatagiven fying alitudeto tat on heground. Determine an aiplane salud ifthe pilot measures the barometric pressure at 27.5 in, He absolte, the ground reports itto Be 2.92 in Hg absolute and the average air density i 0.077 Toa ¢= “2.14 biker scarring a barometer that measures 2.92 in Hg absolute the base ofthe ‘mountain. The barometer reads 25.Sin, gan hetop of the mountain, The average it deny 4 1076 Ibnvl, and gravitational acceleration remains cossane st 32174 isc": What she mountain's ight? "2,18 submarine scrising 500 slow the ocean's surface, Determine the pressure onthe Submarine’ surface if mosphenic pressures [47 psa, the density oT seawater i 68.2 Tom? andg = 32.174 fysec™ 2.6 A versal htionlespstonyinder contin ara a pressure of 50 psa whore the aumespheric pesire 147 psi. The ameter the piston Ui, and g= 32.174 flsce: Determine the pistons mass “217 A vena, tionless piston, similar to the one ustated in Problem 2.31, ‘containsa gsaran uaknowa reste, The piston nasa massof20 bm andacrots- ¥,. From our previous experience we note thatthe system has done work on the surroundings and that the work is postive ‘We would find this qualitative description somewhat lacking if we were asked hownmuch work wasdone. We know that work was performed by the system: now we ‘must attempt to model, with a mathematical equation, what is aetually happeniog, We must remember that this isa model, not a desertion. Hooking back to Chapter we find thet properties such as presse ace defined conly for equiliium states. The pressure must be uniform throughout the system, ‘This is useful, because the pressure scting on the piston face wil be uniform, and 3sa (HAPTER 3 / CONSERVATION OF NASS AND ENERGY pressure multiplied by an area vieldsa free. Consider what happens when the piston ‘moves a distance, dF Firs, there wil be a drop in pressure, and then, according to fur model, the pressure will deop uniformly throughout the system for mechanical ‘equilibrium. A process is called a quasi-egulibrium process when the system i in scuilbeium (e., mechanical, thermal, chemical) at each point going from isinitial to final state. Our model wil be valid or not depending on whether or not this assumption ean be made, [t turns out that this assumption is reasonable for many’ process, beease the time the substance requires ta establish equilibrium is usally much les than the time of the macroscopic event, the work done Using the quasi-equilirium model, the force, F = pd, and the work done by moving a distance di are Bi = pa dt ery however Adl~ dv ow= pat 015) ‘Te total wos is found by integrating between positions 1 and 2; we fon foo 16) The reason forthe inexactness of the work difecentil is that work is @ path function, This may be seen graphically in Figure 3.4, where is denoted by the shaded area on the diagram. This, however, is for agiven distribution af pressure with volume. I'he distribution were changed 0 that of straight ine between states Land 2. the 430’ would be greater, indicating that work isa function of haw the pressure ‘aries in going from state Ito state 2. The J operator indicates an inexact diferential, ‘hich approaches an infinitesimal linn, rather than the exact differential, which appraaches 20, Example 3.1 ‘The pressure ofa gas ina pston-cylinder varies with volume according to (a) pV (6)p¥? = €. The initial pressure is 400 KPa the intial volume i 0.02 m?, and the final volume i 0.08 m?. Determine the work for both processes, Solution Given: Gas pressure ina pistomylinder varies as. function of volume Find: The work done in the expansion process. 42 aNtRoY Fons 55 Figure 35 Assumptions: 1. The eas undergoing the expansion is a closed system 2, The expansion is in quasi-equilbrium as the pressure is continuously defined «during the expansion proces Analysis: The work is determined by imeprating equation (3.16) For the funetional Felationship for p(V) for eases (a) and (6). Case : Won Foem(y) 11.094 Cantante Wp, ,— pas = (400 KN/m"Y0.02 m) ~ 25 KN/en2}0.08 m) weou156 CHAPTER 3/ CONSERVATION OF MASS AND ENERGY eeeereromes Comments: “The spreadsheet yields the following results 1. The area under the (¥/) curve represents the work done bythe gas in the expan son process, The magnitude ofthe work terms in cass (a) and (b) correspond to the graphical areas. ‘The sign on the work is positive, indicating the system did work on the piston, moving it out. 53, The gaseous substance did not have to be specified as long as the pressure's ‘neforl aot as Lage ; = 4, Thegaumptonof geustequleium pees isky tthe wot. as presure : Irate contnuous deter thoughout epension poses tote he eres — work function, = § ree Solse Example 3.1 numerically on s computer using a spreadsheet program. Solution Given: Same as Example 3. Find: Same as Example 3.1 Assumptions: Sarne as Example 3.1, Analysis: “The work can be computed by summing the work over small nerements Of volume change. The work in each volume increment is approximately the average pressure multipliod by the volume change. Case (bie Case (a: Enter the following es Enter the following equations and data into the cells ofthe spreadsheet: ions and data (aicaa) faa‘CHAPTER 5 / CONSERVATION OF N4ASS AND ENERGY “The spreadsheet yields the following results: Comments: |. The numerical solutions agree reasonably well with the analytic solutions in Example 3.1 2. Toimprove the accuracy reduce the size ofthe volume increment, increasing the number of steps over which the work is summed, = Let us now consider the quas-oquilibium process in more detail, Cans the piston-cylinder arrangement in Figure 3.6(a). The piston is held in place by amass acted upon by the gravitational field, hence a force, we move one block ftom the piston as in Figure 3.6(b), te piston will shoot upward and oscillate up and down before reaching an equilibrium position, Clearly the pressure is not uniform during such a process, and the process cannot be called a quasi-equilibrium process. The next step toward reaching a quasiequilbrium process isto divide the mass into smaller and smaller quantities. Figure 3.7 illustrates the mass being replaced by'@ stack ofcards.Aseach cad isremoved, the piston moves upwarda slightamount and after a very slight osilation reaches is equilibrium state, To improve this process {even further, we must make the mass ofeach card infinitesimal, so thatthe change te piston height would occur in differential steps. This process is imaginary, but i represents the ideal, that is the maximum work possible: all the energy goes into moving the piston and is not dissipated by the piston’ oscillation, Note also that the dition ofan infinitesimal card 10 the piston Would start the processin reverse. This rwoceseigealeclan equilibrium ar reversiblepravess. In Figore 3. we could not slide the mass onto the piston testa the process over. This processiscalled an irreversible process it cannot return to its original state along the same path, There are many 3.2 ENERGY Fans 59, Figure 24 Piston movement when lige weight incre ‘nents are removed factors that render a process reversible, Nonunifarm pressure in the system causes the mass to move within the sytem, using energy that then will nat be availabe for work. Frictional elles, 100, are apparent ireversibltes, The energy used to over= come mechanical friction isos for useful purposes. Ako, Quid viscous fores, thats, fluid fiction, dissipates useful energy. There are other causes of irreversibilities, bot the effect is always to decrease the useful energy output oF increase the enersy required. Measuring how quickly work is accomplishes gives us another quantity — gue a7 Piston moverneat when faesial welghis are 1s ‘oved, modeling a quas-equilibsu proces‘CHAPTER 3 / CONSERVATION OF MASS ANO ENERGY Faure 3:3 A hoop with a soap fm. This demonsrates he fet of sutace tension, power, tim 2 enesey/unit time en a ‘One horsepower is defined as the ability to pertormn 33,000 Rb of wor in min 1 np = 35,000 fetofmin Other common power equaiis are Tho bp 2545 Bru/he 746 kW Te SI unit of power the wat, Thus Ljs= Nemest=1W Associated with work and power istorque, Torgueis the turning momentexerted bya tangential force acting ata distance from the avs of rotation, Torque represents the capacity to do work, whereas power cepresents the rate at which work may be one. Section 13.9 explores tarque, work, and pawer in more detall, Forms of work otber than mechanical work are seldom daminant, but neglecting {hem can lead to error, For instance, a film on the surface of a quid bas surface tension, which isa property ofthe liquid and the surroundings. The surface tension of «film isa function ofthe surrounding medium. A simple experiment iustates the surface tension action. In Figure 3.8(3), the entire loop is covered with a soap film. ‘The film is punctured within the thread loop, and the surface tension ofthe fim gets tomake the semainingareaa minimum. The surface tension, o, has units of force per unit length we 22 EvERGy FomMS Bt “The minus sian indicates that an increase in ares results in work being done on the system. The units of work are correct. Thus, we have seen that when pressure with “units offoree er unit area acs on a volume, work i performs and nov we se that surface tension acting on an area is work, Surface tension isan area phenomenon, ‘whereas pressure «volume phenomenon, To demonstrate another form of work, let us consider a wire as the system, Stretch the wire within the elastic limits, and the work is done on the wire by the Surroundings: Fis the tension, and we- fra any wer the minus sign indicates thats pov displacement res fom work being ‘pple io teste, Uwe limite problem to wih she etl, where £1 themogulsofeascy ss theses else stain, ad. ie seb The heat oss =~ 1.3 eg. The fist aw for ated open system i O+rilh+ ket poly H+ rit +ke + pela Divide by and solve forthe Knee ener out (ke =o+ (h,~ ha) + (ke), +(e), —(Pes} = 4+ (hha) + (ke), viii? 7 oem? Rrto0g) sped ~~ PK 025.0 — 6600 Ke Fg v= 724.1 mys Comments: 1. Theeffect of heat transfer from the nozzle reduces the velocity ofthe airexting the nozzle, as that energy cannot be converted into kinetic energy. - 2. Iti important fo maintain correct unit balances in converting specie kinetic energy fo kilojoules/kilograms. 3. To obtain work to or from a contro volume, shaft rotation is required, There will never be work from a nozzle, as no shaft is present. Es Example 3.8 ‘Awwindrnil has blade diameter D and receives air witha velocity vand a density p, The exit velocity from the blades can be considered negligible. Derive an expression for the maximum power thatthe windmill can develop.CHAPTER 3 / CONSERVATION OF MASS AND ENERGY Solution Given: & windmill receivesar ata given veloc air to produce power. and uss the kinetic energy of the Find: An expression forthe maximum power that a windmill can produce. Sketch and Given Data: Figure 3.20 Assumptions: ; trol volume encompassing the windmill's Blades i open. The con Sueady state, steadsflow conditions exist. \ 43. The exit velocity from the blades is zero. oe Feet wh notemperstre eens and the sistem 5, ‘The ehange of potenil energy is 27. The change of enthalpy i 20, a8 tere aos the conto volume sveen the surroundings is na change of temperature or pressure Anais “Th fs foram open syste “eri ke + pela Ht mI Ke. + pee oe B= riley = ig) + [lke ~ Chee] + pe = (PedsD) 36 FURTHER EXAWPLES OF ENERGY ANALYSSS 63 ‘This is not sulciently reduced to determine the poser: the conservation of mass can be used fo write the mass low rate in terms oF measurable properties, Thus pv and the area may be expressed in rem ofthe diameter as Substituting these into the expression for power yields w= Z pp'y Comments: 1. The windmill power isa function ofthe velocity cubed, 9 windmil power is very sensitive to velocity changes, In actual windmills air has an exit velocity from the windeill bisding, which reduces che theotetical maximum to 59.3% of the value determined in this pro Jem. Ths is developed in Chapter 17 5. Enthalpy isthe sum of mieroal energy and pressuredvided by density. In this eave the pressure and density are constant andthe internal energy fair, afunction of femperature at normal atmospheric conditions, is corstant. Ths their change !ang the consequent change of enthalpy is ero 3.6 FURTHER EXAMPLES OF ENERGY ANALYSIS ‘One ofthe most useful features ofthe frst law isthe ease with Which tea be applied 10 a wide variety of energs-consumption situations, In the variety of energ)-c0m sumption problems facing society, thermodynamic analysis, even a simplified frst law analysis, provides great insight. f Example 3.9 A hydroelectric power-generating facility is to be created at @Joeation that has a change of elevation of 45 mand where the river low rate averages 227 mis. Deter- ‘mine the maximum power that can be generated in adiabatic hydraulic turbines Tocated atthe hase of the dam, The density of water is 1000 kg/m? Solution Givens Water flows through a hydraulic turbine foeated at the base of adam. The ‘water decreases in elevation as it pases across the dam, Find: The power produced hy the water Dowing through the turbine3.6 FURTHER EXAMS OF ENERGY A 8s 84 CHAPTER 3 / CONSERVATION OF MASS AND ENERCY e220 pe ob Figure 3.21 Assumptions: 1 The ces i aaa 2 2, The only energy property 1 ‘Velocity into and out of the systern will be the sat hota ll be zero, In addition the internal ene seater ino and out of thesystem will be constant Perform a fist-aw analysis on the control volume shown i Fi 4 rift p Ke + Dean the heat loss i ze. . that will change isthe poteatial energy. The waters me, hence the change of kinetic zy, pressure, and density of the Hnence their change will be zero. igure 3.2 Analysis Ot rut ptket pele i Rearranging the terms yields sre tye 00? i= ri (ped (IT for he mas ow rat from the volume flowrate using the 1+ Ge) Aken + teed @edD density relating the sove! t= Pp = (227 m/s LOO kgs?) = 227 O00 Kays (pee), ~ (peda wile — 2) = 8 rnsPVE5 em) = 44 J (277 000 ke /sK4t J/kg) = 100.1 MW Comments: andthe turbine wectninate dang the contolFoundary around the ing andthe init © ee Sipe eae ern an yee a os ah ed re cna econ aes se chang tage, Compa the work performed pero 2 Thea a ayo atin Eampe 3.488 bilo = 1128.98, i a | Li tempers Figure 3.22 Schematic cagram ofa poner: era pradecing ele we see an order of magnitude difference in the thousands. Thisis typical of most renewable energy sourees; the work thatcan he performes per unit mass is ow, 39 it takes enormous numbers of units to reach values useful in society. The ial costs and sizes are quite large eorspared to coaventional energy sources a A thermodynamic eye has special usefulness when We consider the generation ‘of power, the transformation of heat into work on # continuous basis, When we were developing the concept af energy being a property in Section 3.4, the eivatign leds to the conclusion that the net heat added 10 a cycle was equal to the net work produced, or oie = “These terms represent the algebraic summation of eat and work around the cyte respectively. Figure 3.22 represents the schematic of a possible power-producing cycle. Notice that we do not need to know about al the processes within the cys 10 perform an overall analysis, jst the flow of work an heat energy crossing the system, ‘houndary The netcyele heat term is the algebraic sum of the heat supplied, which is positive. and the heat rejected, which is negative. Ths, the net-evele work becomes se On ~ One (6.53) Physically these terms represent the net work produced by a power eye, suchas the electrical energy generated or the horsepower produced. The heats supplied by ‘such energy sources as the combustion of oil oF coal, of nuclear reaction. For an automobiles engine, & posser pkin, the heat rejection occurs primarily from the radiator to the surrounding atmosphere. For lager power plants used in the gen- ration of eletrie power, typically the heat reject is discharged into a body of water, (Often we are interested in how efficiently power is produced, how well we are converting heat into work, The effiency, isthe ouput, or desired effec, divides by the input. or cost of achieving that effet or (6.55)36 CHAPTER 3 / CONSERVATION OF MASS AND EER sce te nese work cn be expres in terms of eat fm equation 3.68), the Sine tn ee eres ems ony Bee - an 6 yo aban See oe) wed ove apply 10 ene enc an ee ations that hasbeen derived. above ag ee The ceney and oe ower an heat us, Hand terms may aoe se flowsas well ato ene Ey TN amnever exceed unity ands usually much essthan at “an eigen oe sen a thermody aries sain Chapter 7 6e Wi begin tose the theoretical Limits imposed on eficienes. een fc verating power using solar heat. 3.0 cs spc eiremet or sneans ower using la Bet | ‘stant investi i joms 36 Wim, or 830 Buu and erearegn The a en he ate seven, The tl power dese is 2 [See ml ton ns aries ase | ottenergy that ms se. Whit impossible to generate power durin he 1s, the assumption is that excess power may De so} lucir { Argo nat eax dng the ote ROU isto be delivered vera night and on overcast 6 the hours of operation and repurel sion oe re -teinsidem surstinntensity fra pentoaiy andthe et Powe Ginn ott produce gente eee of hat la rnd Thenet het ow thats ogied andthe land ace hats erat Slee. the solar energy forthe plant Shetek and Given Data | (Cite [Lae gg 20507 i igure 323 “dsumprions “The power prose nS can be verb over a Ee HOU of the year. 4.5 FURTHER DLAMPLES OF ENERGY ANALYSS — 87 Analysis: The votal heat low nto the cycle can bedetermined fom equation (3.65). Jig 9.95 2 20.000 KW 2, On Thus, G4. ~ 80-000 KW “This value represents the heat ux at any momtent. We now must find the total heat supply (subject to our assumption) cequted for the yea. On “Thisenergy comes rom the 3000 hofincdent solar radiation, whieh hasan intensity of 1.36 KW/n?. Using the relationship betseen radiation intensity and heat in samely (30 000 KW(24 h/day)(365 day/ys) = 7.008 X 108 why Ober = LFW /m=N3000 b/s0N-4 m4) yields (80 000 kwh) = (1,36 KW/m2)(3000 br m?) A= 171765 m2 = 42.4 ares Comment: Thisiscertinly a staggering land areata cover with collector surface. an inherent problem with large-scale solar eleceie power generation plants. For water- eating ystems, however, paral coverage of a house roo with collectors will fen provide sufficient atea for the domestic heating requirements os ff Example 3.11 powerplant produces 1000 MW of electricity and uses residual oil asthe fue. The oil has 2 heating value, the maximum energy liberated in combustion, of 43 000 KI/kg, The overall ficiency of the power plant is 52%, Determine the instantaneous heat input, the daly fuel consumption, and the dimensions of a cylindrical storage tank (E = D) to hold a 3-day supply of ai. The density of the oll is 980 ka/e. Determine in addition the amount of heat rejected to the environment Solution Given: _& powerplant operating on a thermodynamic eyele produces power while consuming energy, heat. The cycle eficieney and the net power produced are given, ‘Find: ‘The beat input required forthe eycle, the fuel necessary in kilograms per second, the size of a tank to hold a 3ay fuel supply, and the heat rejected 0 theCeuAPTER 3 / CONSERVATION (oF MASS ao ENERGY ‘Sketch and Given Data S=Dii,-uormw Fgwe 226 CCONCErT QuesTIONS a9 “The total mass for a Slay supply i m= (44.72 kg/(3600 s/\(24 h/day) day) ~ 1.159% 107 ke ‘The density relates volume and mass, hence the total volume required i (ng) /in ko) Vm (1.189 X 107) (990) = 11 208 m? Lastly, the volume of a cylinder is = n£D¥/4, thus forthe cil tank with L = D, 11 pm) Ds D=L=246m Comments: 1, The uelandairare not part ofthe system: they only provide a meansto obtain the heat input. 2, This example illustrates the tremendous mass of fuel that must be transported, stored, and consumed in a power plant with excellent overall efcieney ‘We do not need to know how the cycle produces the power to determine some of the overall effcts, such 25 total fuel consumption and the heat rejocted to the 4 The heat rejected to the environment is wsually to a water source, but may be Aireay tothe atmosphere via cooling towers. a CONCEPT QUESTIONS Assumptions 1 The power pant operas J Ab Gener brated hy buring the fel is ficiency, equation (3.65), the heat ena thermotariete : is converted to heat into the system. From the expression for the eyele Analysis: rut may be determined, Spat may’ be sna On Q.= 193 MW From equation (3,68) we can determine the heat out Wg = Ou ~ on Osa = 1923 ~ 1000 = 923 MW ated by burning fuel, thus a= iar “stereo the fel ow atin hlograms/second and gps the heating value of the Teer ade he fel we ate may be soled for 1 928 000 KW = (rick 43.000 Kk) ripe 44.72 kes “The heat input i ee Whats the meaning off work? What does adiabatic mean? Why are kinetic and potential energies dretly converte ato wae? | Whats the diference between steady fw and steady sate? Describe whats meant bythe ineral ener of substance, Explain the sgn convention fr eat end work Describe power and how it differs from work 9, Why ae hea and work not system properties? 10, What dows the area under the curve on ap digram represent? HL, What sa quasieaulirium proces? 12, Why isthe work greater Fora reverse proces tha for an aetoal proce 13, Dessrbe conductive hea tans, 14. What s Neston’ of eoolng? 1. Desenbe raiaiv heat tans. 16, Aa automobile aceleats 1 6D mph in 12 sc 1s the work ferent if aecelerate 10 0 pt only 8 se? Why? 17, Ieivahot summer day, A student laaves hs doemitory room witha fan on and with the ‘door and windows closed, When he rsturns inthe arnoon, wl he rom be warner oF ‘ool tan an identical room without the fan? 1 3 4 §. In your awn word define har and work 6 z e‘CHARTER 3 / CONSERVATION OF MASS AND ENERCY proptems (Si) am absorbed by the brakes in stopping the crane. “ GewianeiSansomoiomeoiace ae ance of 100m, The works found te eg edna ap .m heordde 29 Euan hepasenat tonto 88 Danie assoc co vas 68.2 KI vis-d-vis the earth's, : siching pilings being driven into the ground. Pion tenes tbe ait thestde culate aso be300 lr The anc hte pk ers Ie tmusuedobe3 m Drie he pentane epledeepatopeae ha Ute pling consdced the atu Find thee veloc ent paartetaece he 2.3mltong. Determine founangieatas ) the velocity when the swing reaches the O° ang - Jinder contains wir at a pressure of 300 kPa, The piston movement is 7 7 evenanl nospherie pressure of 100 kPa. The air moves the piston anc an VDuume changeit 0.15 m* 1060" Deere the wo nes the ce Sprines dest proportion to hedopiacencer (tetanic apne eons 7 tne resisting forse: (b) te resisting rag) force itis proportion 2°? ovsito nseiciob tm andcung hs res ace pe Sphere diameter. Determine te work done By the pa a ‘sLjig The ig exsoatLet 84mig and He mis Beenie te Sa 34 a V/min of air with @ density of 1.26 kg/m? and a pressure 1 tim an eases ns eas fab nena Scena ergo espe odie wel Erie Nedesnrchangs nen oes ce ante poe mk A mpresses 3000 liters/isin of water from 98 kPa to 300 kPa. The It theme ate pgi om oho to ear es {em Determine the pump power in RW PROBLEMS (3) 94 ‘MM Tyo stows seams conning the same Dl enter iv chamber and eae as 3 pre ebigae Feng ere ERC Condion ae Spee ete Gano tann fatihestond sth eetancecondiion ane dscsm en ee are eee usaM cxdton it, 1S) mvande “Oem pareine (the eal mas fw esving the cham ot eens nea “HS sailed 4g ox fl romabatoos3.Skm abowiheeats, hac Istheobange in internal enriy ofthe box art hs ithe ears eetna MB 4 om lunes. withthe You's medals) a he mete equal te eer ach atleathoFsmondiseadalsijenaiesren ee ea Detcmine the work cane AP poplin: fommady boing Masha 2 Gemdinecr ice tein agate fay in eno mating he bat Tiss Sen, R002 Nr. Fi the tot ste work ued ale eee MSO mehosem connie ata cxpuns soy in apsonssdnge onceey ia and fon ictal lume 70:80) Demin ths werk daar ee a Fin meade Be PRC pF aCe pr ome aa ene isin and in XPa 5.9 fa lesor on the thineth Nor of aa ofc bulng when the supporting cable ines ae ar srPe etal tothe gourd whore steal ae ne ee Demin (ee aor mas 2500 Landa Wa ake est) e potent ene a thee bie ie ae ee ee ‘and a ene Before impacto he ene change cic eye thes sae ful compose 220 SSL ERONS eo anderson a eerie rosea whi 304 hea i rejected Beenie nts om 0.14 100085 mi Te passancoen Paeerin (he change in icra ener of the ses) ese A31 Se es ith ay ow of37 kg anda inital pero og init fee lens al tsi O60 ms adam nel mere Tosi ann at 22RPS POSS Ag mam oom and so eT "ots is found o be 18.6 We Find the owes ae 422 A Remeubeoticeat'Cmekswhile beng ace to coolbeer sa sou atthe beach, The an theo RU ea O°C 6 LO emg and iat ahaa ne EP Hit any work don be sinew nama he eso the im andthefislanemhalpy af 3007 Kike ‘The gneseaving ie Suracehaveamcathips rechg a, te 17K aa fc. Water Seale gees em wall day? EMH THe owe eur 26 KW ofa What he conse ay? 134 comer compres with an ema of 965 b/ky toa Presure and comprar neat o7SA hg. There are eS heuer SERIES asthe ale pases through it. Nepoting Lina oon oe fine the power requ fora ae miss Sow of Ld ree 398 0 sc omens cis 94 kp of seam with ently of 26% Wg. the henrvanueeed jo iuldandleneswthanentlpyof 60S) e oti ae ee “atearsered fom heweam (Conger patcstincah hea2 uarren 3 /CONSERUATIN OF ASS AND ENERGY apunoun ote; weve he water epee inaesesgm 1 CA Aso, ankgonn fay oF ner wil sorb #2 4d of ener ner see tomes ibd the cooing ater No ae sae Sam oneravutine witha presse of 4826 120500 2691 gad Steam ees ater 252 = 202 A ia on of 3 Sf cal 020.3 B/N Ee pyaar) he iletpeivolome: (2) the exit slot ithe a area 8 0864 su secmnina dow ae of 3ooupetsanadeba nt sms. Sec ID gana cc ea ce kg The exit 2 a (3.8, specie votume™ 089504 an itera energy = 2263 Tue, Deterine the exit weet sae Actjectr assed on tam osomatesasanens of BOO theboilera AE Ee entering aren i enng eras om ae panor Tee Bus dscns arian 8 gin f steam enters at 1378 KPA Wi 4M ETS 2380 SH eee eetnee TITLE cae TNE SAE ee a a al itera St i ana pecs vluse of 0001024 NT frat 0 crs of 203.8 se cnngrsnntc ener Desi aC TE renter ink 4.29 aseadyton stm eens gsofassiaanse wih 1000, = 500 ¥Ps PZ eign v= 50 ms So aa oss oT 10 KS kg aa the Ms esta Or Upmnny 08 w7kg pom 1ORPR AT ou fe Determine the power ab de ent speci internal ever 4.20 Determine the power dtveedy ash asin 20 evelnon et secondagainsta fonstant toque of 19 sat posters ofan engine ifouna abe £9200 St /200) en between Te tora ofa ni 20 in ese Deen FOr a ae OLS saan ane cher can rose 3A at 12 and chars bates 2B WS whe sign Tne caret sey ie at aconstant lie 0 20 sccoring Toe creme 2p ampues and soc Coats werk Fr ‘ist sau me compresad accortingtothe eaonshipg = 6Y 4 000 Pan? a a a vIn ST ee a ee 2 et oc ying te expression or resus HOSS the the oe oor aga, and finding the are unde suas nesenonndina isto oman ns ress 100 Bas 10 volume of Ascend of Pa wletowng eee ee? 2Y +b, 0.15 109 fe Pm an is conta Coleus te Rok peor sab ephrl talon consis a at SO MPL ad 3D. Ft 2 sett pester ere Hea agi he Ban 0 the volume roporvena oman te work done bythe Balloon. Assume 1 arene wrk ied cee 100 88cm 101280 nh onal ‘Ghose he elevation increases by 35 8 L ProsLens (a) 93, ‘cm from its extended, rest pane 3.39 Determine the ote ho ce eaeea eee cer eames sn 1¢ minimum power required to accelerate the car, se momsdians trap ate ee tee nat ejezaipen lesen kee eas kp Bees youstest hgh catiny the paca se craton 3.7 mis Detetsine( ston 97 eerie et ei eit (us sae ie pach he operating rosy whe ei cause of the heat addition), 10 KI of wort meals there 2000 hes one rom 8 Fie he mining dats nthe we eo fra che sem shine om) wi) EIA) AE) 20 wo 23-7 > 8 4 m5 . 8 6 und the system performs 70 kI of “aprewon S04 ofwerk ‘sacl to he Sy Determine (a) the heat transfer during th oe meri hac and net heat transfer for the cycle, mthesecond races) ihe poe sess the sytem rejects 16D KI of heat, Determine (2) th rks Ata rom conn gf °C hd 15 minby is Tcenapy ora ira C8280 agndat eC WORT AG Wh te eat os from the room is 120i Seti er han DA, Drei tee oe rom a each °CcuapTen 3 / CONSER NON OF MASS AND ENEREY 4169 A student living in he home desert in Problem 3.68 dees to invest ina solat 2 ude ne Chctacy of 0% tat occupies one-half ofthe cot are. If he home ce oe hoa kg off with heating vale of 3 00 kor seating. what wil be ts anal savings it ke i? 4470 taking slong a dvr an engineering dent notices the ste of former sal that re al eo pace, Revananis fh oil dam ae sti visible ang the tear is sil Henne erndcnJeidestomaesome measrementsanddewermine the asim owe dteuldte gencrated hese weredesloped. Te stream ow fous os Toe ta henge evi sm. Determine the maximo pows that could ibe produced PROBLEMS (English Units) ‘an Asystemundegoesa cle where 10 Bu of beats removed and 15,000 Bab of works are a apeem doe he fist proces. Inthe second proces 15 Bas of Reais ore nat the work nsctsar 19 complete the ple? #5. Acosed stem expands fom $10 2.5 the pressure varies aecoring 197 To pas Determine the work 43 Catelae the Kinetic ener of 50004bm automabile moving at 69 ‘hat A tid 10 psi, wth pei volume of 4 fomanda veloc of 00 see enters asa tox from the deve by radiation i 10 Bufo. The work Gone bythe ee Apron The Mid eits a 20 psa, 5 f0/Abm ang 1100 see. Determine the change inspec intemal ners “eas am air compresoe handles 300 RY/min of sr wth a density of 0073 Toe and a A STP pa and cecaras an pressure of 75 psi with density of 208 Pea ponoc napoli internal energy sezossthe compresoris3$ Brom and anc Was ty cooing i 10 uli, Neglecting changes in Kinetic and potential ‘erp ad the poser in Bau hp, and WW. a4 ‘Two pscouestcams contsning he same Fugen a mising chamber and ean a2 TRS EERn Tor neta gs theemrance condons are = Din = 4 fe, ane sre 0 Tom. Forte second gastheenrace condiionsare 4s 405 r= a wali and oy 8is fis. The exit steam canditon is ~ 40 se and rane ieeisne a the total mass Now easing the chamber, (b the etc of 2. 1.7 Seam witha fw rateof S00 Ibm/hemersan agibatic nee at 200 sa 600 min sae cine wun cf 2 36 (bm, ans witha specie intra eneray of 11227 re eee cae contions ar p= 20 psi, spetic volume ~ (7.6 fom, and Thteveal energy = 973 Bulb. Determine the exit els: ag A gaiscomprenedaccorting tothe elaonshiny~ afb where a= 1000 pi ee oe be Thelma volume s0.t andthe inl vlunssis0) (Determine aoe esac dpe inthe proces by integrating the expression for pressure, ploting he Whine oma ye dag, and nding he area under sore sag agusenpandsina pston fom an intl pesue of 1000 psi and an ina voleme of FRORLEMS fopis9 Unis) 97 50a se 2 in wl flow roses ey vagy tte aad iat ae en re 4s alin conn sat 8p nd 35-R.Frrore the ese operant aretha Heats aedeiothebaloo andthe an ee ‘Determine the work done by the balloon. Assume d, — 1 a ae emit work eure acer a 2000 fm ero 140 “where the elevation increases by 100 ft hosinabonahit ‘342 Dati the work neces compres ina onan Din adance of iin ore wexendodrstpgcon eae? 3.13 Determine the time to aceelerate a I-tom automa earning ime i rom rest to 80 mph it as “314 4 000-bautomobiltesopped at al i is stopped ata walt ight proosing ina dieeonupa20" Thelenghoten 20 athcraceatston wot npn saison emne ‘the minimum power required to accelerate the car, “ While sanding inline oF # iH, you decide od Dons sang a you decide to detente the minimum power ‘uted nope thin ome toma eile tothe ope. ani cvaon ines E00 You tims hia ‘este ri 9 Rg You er ena es two occupants are om. Because you are at higher elevations, the ational ‘acceleration is 31.2 fsee?, Determi reopen ihe eo) 5312 mse Determine the power ees to Opa (9) ‘ing this vale af ower, the ime equied eo sng thse afpower thecmerequed ork heaping ety Wen Be 3 3.16 A serial piston elindr assembly comaining wate ‘hrc 1B feat stance iw Ine ate eapensonpes {Geena he ea aon) BODO Rb worksdone, Alun thee 0 Bue ss font em Whats aera ofr sa lf He et aon “3.17 Fill the ising data inthe able below for a closed syst shangng fom ste | 49 eeu) We Feu) eGR) AEG) 2 aaa 30 7 a7 " . 8 » © Is 8 io "218 A system operates ona ono-poce 1 process cycle. During the fst proces 6 Btu of eat echseldtnesn tothenssnpetoa cafe nese os proces (0 he et workand neha wane ibeges 139 A.ysem operates on three-proces cele. The ist process is adiabatic, an 60 Bea of ‘ork isdane on hestste. In thesecone proces no work occu, Out 240 Bt of heats(GUSTER 3 / CONSERVATION OF MASS AND ENERGY ess In the thied process the stem ree 160 Bu of et, Deteayine a) te work, uk or isan proces (0 the net waek and net hea transfer forthe eel 1:00 A tng adiabatic oom containing 700 hm ofa 2 6O"Fisheated to 80°F in LS mindy AROS Taster tnat consis of «200 Tan pushing 2 Ibmiee of ar aos electric Sega Threnthatpy ofthe airat 60°F 6124 Butbmandat 80°F 129 ebm. (Wises the tte of Bet transfer io Buin? In KW? “The heater in Prsbens *320 i now located in aonadiatatie room ofthe sme ize The hoa ose fom the oom ound tobe 20 Bm Detnrne the tine forthe your io ee 80°F fromthe inal 60°F. 5.2 4 1500 W electric hie dyer is evenly an adiahatie uct and consists oa smal fan dud owsaisorera eating element inceasing he temperature of the a fom tint eapenatacto277-Ftoanestemperature of (27°. The i density ant conditions wee tpt ant at outet condita 0.0709 in/ Thespecie internal eneey ‘Seenges tom $1 8 Beal ltt 201.1 Buylbm at outlet, The pressure temas cere acd? pl titoughout the hr yer. The eit rosesectional asa ofthe it rlsrutcn he novale win places |p Deterasine(a) he mas lw rate fai thous Seer te selume ow at fara ile conditions (the velecity ofthe ai fesving the nozle 18:28 an electric hopnater heater consis of a 24niameer pipe containing a eistance Meal hener Cold water enter the pipe at 40°F with an enthalpy of § Bylo and Fee GD ith amenchalpy of 108 Baby. The wate os ates 3 gal/min, and Feasin, 624 tomy Detemine the rating of eect resstance in KW and the ‘locity oF water sein he pipe “2.24 4 10sip pump draws wate fom a wel 30 belowground level and scars itinto a Suter Weer sop a bulking 800 & above around. Theres no change in the water's eee arenes temperature, poesure or speife volume during te proces, Whats th enum Bow rte pssbe? The pamp may be considered adiabatic, and the tds of waters 624 Ih 12425 4 ob masses down a ramp incined at 48° from the horizontal a otal vertical Godaneeot 0 Determine the ekvty of ass when reaches the bottom, nepeting Thtion and ai existance 12.26 foveeupsied 0 LOD masintally at rest fr 1S soccausesitto aveerate 10sec" ‘ving is time pes, stern dhe workin +327 Aircontived ina pstor-slinder underges two proces in sere, the fst the ait Res aEeae Sting to pl= orn SOO pea anda specie volume of 444 Ahm toa SeBStursofa0 ste Thesecoae provesisaconstntpresiré compression unt speci fume gate speci volume L Skete the process om a 7-1” diagram and deter 138 Air conaine ina pston-slindsr undergoes so proves in series. tn the fist the ‘Slum remains constant, hie the pessre decreases from $5 psa 9 psa, AC his saint tic umand proves pl! onus, pressure increases 0 45 pi, and the Gna Bolus 50 Sheth proeses om ap cigrant and detenmine te workin BR “he folowing nesstrateste variation of pressure and volume the eine fan internal comburtion ensine dufieg the exsension paces 8 PROBLEMS fess Units) 99 Date eint Pressure (pia) Volume in") H 350 2s 2 230 31 3 210 3 4 5 so 5 110 70 6 50 120 Plo the data ona diagram and determine the Work doaein fb Isthisexsetoran cstmate? Way? #5.30 An indus frnace has a S-n-thic, 100A beck wall. The bricks have a thermal Conductivity of 2 BuuyhrfeF and havea uniform and steady temperature on one Surface of 70°F and onthe other of 1200°F Determine the ea transer through he ‘all. +331 sutice ofS 2 with an emissivity of 85 emits thermal radiation. Find the radiant heat emitted for suracetemperautes of 77,277", and 77°F 3232 Retiigerant ows through 6, 0S4n-diamecer tube and evaporates sts constant temperature of °F The tube’ Surface temperature i oestart a 10°F, and the unit Comectve coofcient = 380 Biu/hr(2F. Determine the raze of convective hes leans Tom the refngerant to the ube sure, £3.33 A windail produces on average 6 KW of elovtica power over an 8h period. The ‘deotsity i weed to charge storage Baeics. nthe chang rocess the batteries increase temperature causing them tofose hea tothe suroundigs at arte of $00 Biu/he Deteumtine the foal energy stored inthe Batteries ing ths she psi, °334 A pistoncsliner contains gasiniialy at $10 pia ith a volume of 1.06 8. Te sis Compressed daring » proces where 91! = C toa pressure of 1235 pst. The Best trans fromthe gos 3.0 Reo, Determine the change in ates ents, eget ‘hanges i Kinetic and potential energies. ‘Anadiabtictank with a volume of & 81 receives padle work ata rate of 4.8 W for 30 thin The gsi he tak has inl density of DOTS Ibm. Deering the specie ‘Volume athe final state andthe change of speci iexeaal ens. #2246 & nonadiabati tank receives paddle work for 30 min. The ower to ze paddle varies ‘sith ime avording to = 12, where Hin wattsand sin minutes. a adaiion| ‘here ihe cane from the tank aa constant at of 170 Bru Determine the net {change of the g's energy afer the 30 min +37 A closed ssten containing a gas undergoes a eels composed ofthe process, The ssten”simtil atest (47 psa, 83.070, andan intereal energy of $40 Bu. The gas ‘compress acording to pV’™ C unite pressure 290 sin and the internal ener S25 Bo The second process has constant volume, and the heat oss 6160 Btu he final process eturing the system tote nists the works 41300 fel. Dete= tine the heat transi foe the RSt an lst processes. 13,8 A teat pone eel with thermal efficiency of Os produces 8x 10¢ bof net work Determine te net aided an heat eeeces for the ce 1333100 13,38. heat poner cycle with thermal efciency of 384 revives 20 10° Buje of hest shite. Determine the at power produced a hp and MW 3.40 4 powerplant with an eficeney of 3% produces 250 MU of power: I ses oa athe Fuelsuppls which hae eating value of $200 Brytbm. Deter the ful requited pet Gay. Flow many tone of coal must be taasponed to the powerplant to have I week's ‘spl of cont oo hana? ‘3a A power pan proces 500 MWW of elect power while operating With a ficiency of {43h The eat eects rom the csepoesints colig water supplied fom anadiacent river, The waters enthalpy ineeases by 20 Brun ast eseives the heat rejected, BBetermine the mas fe rate of water required 43.82 south-facing roof ofa home measures 25 eby 40 Nand eeceiveson average 2800 h/st Grsunshine with an average solar radiation of 430 Brufe-t-F, Determine the i nergy oceved by the root anual 1343 A student living inthe home describe in Problem 73.42 decides 0 investi a solar oer with aneicieney nf 8% that oesupes oneal ofthe zot are. Ihe home nual uss 1000 gal of i with «heating value of 18,000 Bu/lbm and a specie privity of0.9 based on water’ density of 62 bmn) for heating. what will be the Sinual savings in gallons af i? 344 In hiking along a nser ae engineering student notes the ste of former sail that Used hydro power Remanansf the oiial dam are sl vse, nd the steam stl flowing, The student decides fo make some measirements ari determin the maxi- rum poner that could be generate ifthe site were redeveloped. The stream Now is Foun be 900 hse, aad Ue change in cevation is 13 ft Determine the masiemuty Powe that couk! be produce mh COMPUTER PROBLEMS {C31 Develop a sereadshost template or computer program that wil determine the exit come “ton forthe adiabatic mining of upto veils streams characterized by area, mass How rate, velit. density. pressre, and specie internal energy. The outlet steam Shout have te ante characte Test using the information from Problem 3.14 (63.2 The engine from Pecks 331 aoceertes from $00 10 1000 gpm ia $s Compute the power increments of Is andthe average power during the pero of aceleation 9.3 Computedhe energy and power used by the device in Problem 3.33 ver the fst nut. Pt theres in increment of 5s (CA Solve Poodle 5.18 except for pa fal usinga spreadheei program. Compute he work ‘merical by summing he average presse over smal volume increments. Compare fhe results for volume fncemens of. mand 0025 with he esals obtained by sales A Properties of Pure Substances In Chapter 3 the concepts of conservation of mass nd energy were introduced. The ssstem energy transformation had an unknowa substance it whase properties were siven. In this chapter you will earn about pure substance, thee behavior, and their properties. This wil include *# Understanding the various pases, sli, liquid, and vapor « Learning the conditions for phase equilibria * Visualizing the three-dimensional po cations ‘+ Developing the ability to use the tables of properties on the computer wel as in the appendix; ‘structure ofa substance and is impli- «+ Investigating how the properties of two phase mistures are determines thee. retially and experimentally100 13,38. heat poner cycle with thermal efciency of 384 revives 20 10° Buje of hest shite. Determine the at power produced a hp and MW 3.40 4 powerplant with an eficeney of 3% produces 250 MU of power: I ses oa athe Fuelsuppls which hae eating value of $200 Brytbm. Deter the ful requited pet Gay. Flow many tone of coal must be taasponed to the powerplant to have I week's ‘spl of cont oo hana? ‘3a A power pan proces 500 MWW of elect power while operating With a ficiency of {43h The eat eects rom the csepoesints colig water supplied fom anadiacent river, The waters enthalpy ineeases by 20 Brun ast eseives the heat rejected, BBetermine the mas fe rate of water required 43.82 south-facing roof ofa home measures 25 eby 40 Nand eeceiveson average 2800 h/st Grsunshine with an average solar radiation of 430 Brufe-t-F, Determine the i nergy oceved by the root anual 1343 A student living inthe home describe in Problem 73.42 decides 0 investi a solar oer with aneicieney nf 8% that oesupes oneal ofthe zot are. Ihe home nual uss 1000 gal of i with «heating value of 18,000 Bu/lbm and a specie privity of0.9 based on water’ density of 62 bmn) for heating. what will be the Sinual savings in gallons af i? 344 In hiking along a nser ae engineering student notes the ste of former sail that Used hydro power Remanansf the oiial dam are sl vse, nd the steam stl flowing, The student decides fo make some measirements ari determin the maxi- rum poner that could be generate ifthe site were redeveloped. The stream Now is Foun be 900 hse, aad Ue change in cevation is 13 ft Determine the masiemuty Powe that couk! be produce mh COMPUTER PROBLEMS {C31 Develop a sereadshost template or computer program that wil determine the exit come “ton forthe adiabatic mining of upto veils streams characterized by area, mass How rate, velit. density. pressre, and specie internal energy. The outlet steam Shout have te ante characte Test using the information from Problem 3.14 (63.2 The engine from Pecks 331 aoceertes from $00 10 1000 gpm ia $s Compute the power increments of Is andthe average power during the pero of aceleation 9.3 Computedhe energy and power used by the device in Problem 3.33 ver the fst nut. Pt theres in increment of 5s (CA Solve Poodle 5.18 except for pa fal usinga spreadheei program. Compute he work ‘merical by summing he average presse over smal volume increments. Compare fhe results for volume fncemens of. mand 0025 with he esals obtained by sales A Properties of Pure Substances In Chapter 3 the concepts of conservation of mass nd energy were introduced. The ssstem energy transformation had an unknowa substance it whase properties were siven. In this chapter you will earn about pure substance, thee behavior, and their properties. This wil include *# Understanding the various pases, sli, liquid, and vapor « Learning the conditions for phase equilibria * Visualizing the three-dimensional po cations ‘+ Developing the ability to use the tables of properties on the computer wel as in the appendix; ‘structure ofa substance and is impli- «+ Investigating how the properties of two phase mistures are determines thee. retially and experimentally102 CHAPTER 4 PROPERTES OF PURE SUBSTANCES 43 SATURATED PROPERTISS 103 4.1 THE STATE PRINCIPLE 4.2 LIQUID-VAPOR EQUILIBRIUM The state ofan equilibrium system can be define by its thermodynamic properties, How many properties are needed to uniquely define the state? We can answer this ‘question using the state principle 2 rule that has heen developed from many years of ‘ShservationsA closed system may have a variety of heat and work interactions; for instance, there could be mechanical work of compression, electrical work, magnetic ‘Work and heat transfert the surroundings. Each ofthe work modes ischeracterized by an extensive property and a related intensive property. For example, volume (extensive) and pressure (intensive) characterize mechanical work. The intensive property describing heat sanster is temperature. In systems undergoing equlibriam processes of that can be approximated by equilibrium processes, the number of| independent properties necesary to defie the sistem is one more than the number fof relevant work interactions. Thus, for simple compressible systems (mechanical Work) in the absence of potential and kinetic energies that are included inthe totat ‘energy term, 9 independent properties can define the state "The predominant system used in this text is that of simple compressible systems, where work isenal 10 fp dV, Should we write the frst law for such a system enaes fra there would be no way to determine electrical potential, for example. Information concerning a system having elecrial work interactions as well as compressible work interactions would require an additional independent propery. ‘Returning tothe simple compressible system undergoing equilibrium processes and assuming it contains a unit mass for simplicity, we can define all the other properties of the sjstem, using tv independent intensive properties. Thus, if we ow the temperature, 7, and pressure, p, other properties can be determined: heh, plum WT, pe v= aT. ps In this chapter we consider simple compressible systems using pore substances. “These substances are of constant chemical composition, regardless of phase. Let us pick wateras the substance in te system. The water canbe iguid solid, or vapor. sve sample the system now, the sarmples wll be distinguishable by the various phases bf water Water isan example ofa pure substance, whick may existasa liquid, asoid, fr a vapar, phases by which all pare substances are characterized. Recall that the Sefton ofa pore substance s that itis homogeneous by nature, does not undergo ‘chemical reactions, and is not a macchanical mixture of different species. The sub- stances in our systems considered heretofore have been phases of substance. The phases are physically homogeneous, There is usually a sharp distinction between phases, inasmuch as the properties of one pase are decide! different from those of| [nother phase. There is eierence between we ana iquic Water, for example Where do these phase changes occur and how ean these changes be quantified and used? To answer this, let us consider the piston-cylinder arrangement in Figure 4.12). Thisisjosta scientie way of considering apot of wateronaktchen stovewith the weightless top sitting onthe water instead ofthe edge ofthe pot, Heat sade at constant pressure, ¢™ Ak, ta the liquid water at 40°C initially, As eat is added, the ‘water temperature rises uni itreaches 100°C; see Figure 4.1(b), Then what happens? The water boils as shown in Figure 4.1(), What isthe boiling process Ita phase transition, The water ising from liquid to vapor. In Figure 4.1(€ ll the liquid has Just changed to vapor and finally, as more hea is added (Figure 4. 1[e), the tempers- Ture of the vapor increases ta Ce ay er ae en a a Figure 41 The change of water fom a Subsoold liquid to superteated vapor by constant peassure heat ation SATURATED PROPERTIES Let us plot a 7» diagram showing this process for 1 atm of pressure (Figure 4.2. ‘When the waterisat point, itisa saturated liquid. Thismeansthatitisat the highest ‘temperature at which, for this pressure ican remain fqutd, Mf more heat is added, some ofthe liquid changesto vapor, and a misture of vaporand liquid occurs, such as atpointe, This vaporisa saturated vapor. Atpoint dallthe water exstsasa szturated ‘vapor. Any addition of heat results the Vapor sbeing superheated, suchasthe vapor at pointe. Ths superheated vapor. The vapor has atempersturegrester than the saturation temperature, that i, the temperature of the water when it is saturated Tiguid and vapor, foraglven pressure. Note thatthe emaperature ofthe water does 0raNces 45 SOUDLIQUE-VAPOR EOULERUM 105 Figure 42 Constant pressure het ation to water phase transition goes into changing the wate eae vane 4.4 CRITICAL Pi err point. This point has a unique temperature and pressure known asthe critical em peratureand eritcal pressure. Atpressureshigher than the critical pressure, theliquid Now let us run the same estat i ‘Now let su the sme test at ifrent presumes and plot a family of constant Could be heated from a low teeyperature to a igh temperature wthout a phase Bese tnesona Fndigram (gue 4.3) Purtermere et uscona he cso? transition occuring This is illustrated by the dated line in Figure 44, whic ills: een oft. These ae the saturated uid fine and the saturated trates the p> diagram forthe quid vapor phases of water At emspertures hat are respectively. The point of inflection, paint fon Figure 43, isthe erica treater than the entcal temperature, the presure may’ be increased 10 very high Values, and no liquefaction will occur. 4.5 SOLID-LIQUID-VAPOR EQUILIBRIUM Let us consider the solid phase of water —ice, We take a piece ofice at—17.7°C and put it ina vacuum chamber until the presure is 348 Pa. We now heat the ice. The Temperature of the ice wil rise to ~6.67°C, and then further adition of heat will (cause the solid water 10 go directly to water vapor atthe same temperature snd pressure, This is called sublimation. The pressure ofthe system for the next case is faised to 610.8 Ps, Again we start with the ice st ~17.7°C and heat it.The tempera ture will rise 10 0,01°C. Further heating causes some of the solid water to turn to liquid and some to vapor. This point, characterized by this temperature and pressure isthe ple point for water. Its the only point at which all three phases may coexist Ir the presoue ts furtber increase from tho initial sting to 1.0 kPa and heat is sup plied, the ice will se to 0.01°C and change to liquid. This scaled melting. These processes ae llustrated in Figure 4.5, Fgure 42 The Tr dingram for water at various pressures,47 THeEOnvensionaL SURFACE 107 106 cHAPTER &/ PROPERTIES OF rune suesTANcEs 4.6 QUALITY figweas Ap-T diagram showing phaseesulrum ins, {ne ke point, andthe ei point. “The amount of heat added to effect the various phase changes is equal to the change in enthalpy, a5 noted enlir, These various enthalpy differences across the phase boundaries have certain names. The change of enthalpy between a solid and Tiguid phase isthe fafens hear of fusion. This is somewhat of & misnomer since heat refers only to thermal energy’ crossing a boundary, but the term was developed and ‘sdopted before this lasification, The change of enthalpy between aliquid and vapor phase isthe late ea of vaporization. Finally the cange of enthalpy in going from a Solid 10 a vapor phase is the latent heat af sublimation. ‘Referring 1 Figure 4.2, is possible to denote the state of water by knowing the ‘temperature ane pressure ifthe waterisa subcooked liquid or superheated vapor. This means the lines of constant (emperature and constant pressure cros at some unique paint, This point isthe state ofthe ssstem a this presureand temperature. However, ‘that ifthe state ies somewhere Between points band din the two-phase epion? The Tines of temperature and pressure are coincident, so they do not uniquely Locate the ‘system state, Hov could the sate be located?” Knowing the temperature and pressure [zNes us one line. Ifthe faction of vapor were known, then we could find out how ‘much water had been evaporated and wherealong the ab ite te system existed. tis important to realize that we need two independent intensive properties to determine the sate of a pure substance, Inthe stturatea mixture region, temperature and pressure are not independent and thus da not dehne a state. This is demonstrated raphically by their being coincident and not intersecting, ‘We now define a quantity, x, called the quality asthe mass of vapor in the system divided by the total system mass (the massof vapor plus the massof guid), Note that ‘the definition of quality presumes a homogeneous mixture of vapor and iui miss vapor ‘ass vapor + mass guid any Let us see then whether ve can find the value af some extensive property on a unit mass basis. The specific enthalpy is desired a: point con Figure 4.2, and point cis characterized bya quality x Let the enthalpy astate be, andatstate dletit hy The change ofenthalpy in going from 810 dis fyy™ fis~ ha. To fd the enthalpy of Slate c we consider first that al the water Was initially at sate b with an enthalpy fi ‘Then fraction of the water was evaporated, inereasingitsenthalpy by fgg. Ths, Me total enthalpy ofthe mixture of tate cis gt has hem he = Oia 25) This hasbeen illustated for speciic enthalpy, but is valid forall speciic extensive properties. Equations (42a) and (4.2b) assume that the enthalpy of each phase remains constan! when determining the mixture enthalpy. 7 THREE-DIMENSIONAL SURFACE ‘Water isnot the only pure substance with whieh thermodynamics concerns isl ‘Another pure substance is earbon dioxide, which is used in reiiazration cycles ond has a Fp diagram different from that of water. One should not expect ll phase 75%. Figure 7 AT diagram illstrtig thre cegons includes fine steam bles Mb) LOD psaCHAPTER 4 / ROPERS OF PURE SUBSTANCES Solution Given: “Te values of pressure and quality of steam. i ‘The values of enthalpy and specific volume at these states Sketch and Given Pata: Assumption: The state isan equilibrium state, allowing use of the property tables Analysis: Case (a) Goto Table A.6 and determine the saturated liquid and vapor values forthe enthalpy and specific volume at 250 kPa: i, = 535.23 KI/Kg, y= DUUT.LRY/AB, fg = 2181.9 KD/kg, o- = 0.001 067 5 mske, ey = 0.718 77 mks, 240.717 me Why ay = 535.23 + @.SN2181.9) = 1626.18 bike op +g = 0.001 067 5+ (0.5N0.7177) = 0,3599 mks “To solve using TK Solver, load the model SATSTM.TK and enter the equations fronting and eee volome i the mitre raion In the Int colunns of the Variable Sheet, enter the values of presse (250) aod quality (S) and press F9. The Iterative Solver will be called, and the following results should appear. 44.8 TABLES OF THeRMODYNAMME FROFERTES 914 Case (0: Go to Appendix Table A.15 and determine the saturated liquid and ‘apo values for the enthalpy and specifi volume at 100 psa: = 298.41 Beuylbm, 12879 Bulb, y= 899.47 Brum, +) ~ 0.017 738 Rib, r= 44339, s8hibe, yg = 46 16 f6jtbm. he byt aby 98.41 + (0.75)889.47) 165.51 Bru/lbm vm ay tity = 0.017 738 + (0.75Y4.416 16) = 330985 07m ‘To solve using TK Solver, change the woitsin the Unit column to Basis, enter the new values For pressure and quality, and press F9. Your monitor should display the folowing results.112. CHAPTER 4 / momen CF PURE SUBSTANCES j | neo Comments. Sketches of the Tv or p- iagcams ae weil in visalizing what region the sat isin, liquid, mixture, or superheated ra Superheated Steam fow that we have a certain confidence in finding the values of properties in the surated region, region Il, let us consider properties in the superheated tegion tegion IL Water vapor exsting in this region must be defined by two independent proper- ties before ihe tate canbe determined. Usually one a these properties isthe pressure, ‘nd frequently the others the temperature. These properties are tabulated in Tables {AT and A.16 anc as TK Solser model SHTSTM.TK. Example 6.2 ‘Determine the enthalpy and specific volume of steam at $00 kPa and (a) 300°C (5) B= 2800 ki/ke, 48 TABLES OF THERMODYNAMIC PROPERTIES 113, ution Given: Steam pressure and temperature, Fin Steam’s enthalpy and speciie volume a this state Sketch and Given Data: Assumption: The state isan equilibrium state, allowing use of the property tables Analysis: Case (a): We find steam with these properties in Table A.?, because the ‘emperatore of the steam, 300°C, is greater than the saturated steam temperature, 151.8°C, forthe pressure of S00 KPa, Procoed to the S00 kPa columns and find remperaiuie of 300°C. At thisine the values of hand sare 3064.2 kifkgand 0.522 72 mfg, Case (b: The internal enerey of steam isnot listed. To determine ifthe stem state i in the superheated region, frst calculate the saturated vapor value afi, tig ly bp 2748.96 KIVA — (300 KN/om? 0.374 894 m? ka) = 2561.5 Khe Since the value of internal encees, 2800 Ki/Ke, is ereater than the saturated vapor valug, the steam state is in the superheated region. Yo determine the enthalpy, specifi volume, and temperature inthe superheated region requires creating col tum for internal enesgy for different temperature values, say at 250°C and 300°C, and interpolating between these, yielding 2 temperature of 298.2°C for 1 = 2800 Li/kg. The values for enthalpy and specific volume would be fownd in a similar fashion Using TK Solver simplifies the solution of this problem, Load SHTSTM.TK, and enter“h = u + Pv" inta the Rule Sheet and the values for Pand u in the Enput colunin ofthe Variable Sheet. Press F9, and the following results should appear.(CHAPTER 4 / PROPER CF PURE SUBSTANCES Comment: Using problem-solving software readily allows the determination of property values other than those tabulated a Subcooled Liquid Water ‘Thistime et us consider water at 10 MPaand 60°C. We wantto find the enthalpy and speciic volume at this condition. We might suspect thatthe water is a subeooled liquid in region LV on Figure 4.7, which has property values located in Table AS, Why? Again we check the saturated water temperature at 10 MPa, Its 311.06°C. the temperatures less han ths saturated value for water witha pressure of 0 MPa, the water is subcooled and its properties may be found in Table A, Since the conditionsin the problem meet thiseriterion, Table A.8 willbe use forthe solution. We go tote column for 10 MPa and proceed vertically down wnt it intersects the 60°C Tine. A this level we read the property values a¢ = 259.49 kS/ke, 0.001 0127 mk 48 TALES OF THEAMODYWANN PROFERTIES 115 Measuring the Saturated Vapor State ‘There are tabulated values for vapor properties, but itis sometimes ver dificult to measure the vapor state, Let us considera situation in which steam is driving a turbine and we want co know the steam sate ast enters the turbine. ‘This means finding the state of @ Dowing vapor. Ifthe vapor is superheated measuring ie temperature and pressure would determine the state, What happens if the steam isa saturated mixture? The temperature and pressure are not independent Inthe sturated region so more information is needed to determine the state There is no erady means to measure other properties, such as specific volume enthalpy. or intesnal ener: ‘There are several methods to resolve this problem, one of the most common being a throtdling calorimeter, schematically illustrated in Figure 4,10. Note that the seam supply is simple fiom a venical pipe. Ich pipe were horizontal, separation liquid and vapor Would be more ap: to oscur, Ina Uottling process the pressure is decreased adiabatically by use of a valve, Thie isa totally irreversible process. A first-law analysis ueross the adiabatic valve shows that the intial and final enthalpies have the sume value. f there i a sufficient decrease in prssure, the steam will be superheated at lower presture and temperatuce “Temperature and pressure measurements can be made for he steam leaving the valve (i the cup). and the enthalpy can be determined. [tis import that there be negligible heat loss and negligible velocity atthe poigt of temperature and pressure measurement. By knowing the enthalpy and the iniil pressute or temperature. the inital steam state may be determined, This is the average value ofthe steam sat, since itis based on a representative sample Other pes of calorimeters operate with varying degrees af success, A problem \with the throttling ealorimete is that the initial seam state must not be very net or ‘throting will not produce superheated steam. A separating calorimeter mechani- cally separates the liquid and vapor. volumetrically measuring the liquid an! mea> suring the remaining vapor ow rate. An electric calorimeter, through resistance heating, supetheatsa sample of stem that steadily withdraw through a sampling Figure 4.10 Schematic digrar of a healing scam calorimeter.6 ‘CHABTER 4./ PROFERTES OF PURE suasraNces tube, By measuring the electrical ener added and the superheated steam stateand steam flow rat, the team quality is determined. Example 4.3 A throttling calorimeters connected to a desuperheated steam line supplying steam tothe auxiliary eed pump in a steam power plant, The line pressure is 400 pia the Calorimeter pressure is 14.7 psig, and the temperature is 250°F. Determine the enthalpy and quality ofthe desuperheated steam. Solution Given: Steam ata given pressure is expanded through throttling calorimeter The pressure and temperature ofthe steam inthe calorimeter are know, Find: The enthalpy aod quality of the steam before entering the calorimeter, Sketch ond Given Date: a0 Figure a1 Assumptions: 1. The throtling proves is adiabatic. 2. Equilibrium exists at the described steam states, so tables of properties ean be sed, 3. There is no work crossing the contro! volume. 4 The changes in potential and kinetic energies aeross the control volume are nenlgible 5, Steady-state conditions apply Analysst Noting that T; ~ 250°F is greater than Ty at 14.7 psa (212), look for the value of enthalpy at state 2 in the superheated steam tables. Thus, hy = 1168.5 Buy/lbm. "The first law for an open system with steady ow is O+ rif ke.+ pede = W+ Mill + ke. + Beda Applying the assumptions, sls reuces 10 hy 449 TARES oF THERMGDMNANIC PROFERTI 197 ‘Taus,theenthalpy atsate | isthesameasat tate2. Inaddition weean determine the quality at sate Las follows. hy = 1168.5 1168.5 = 424.38 + (4781.08) x= 0.953 oF 95.3% hy + Xily 'SATTSTM.TK can be used to solve the problem. Input the state | enthipy value and the pressure; the program determines the quality: You sill need to perform the firstlaw analysis to realize tha the enthalpiesat state | ard state are equal basedon {he assumptions liste, Comment: The toting calorimeter is useful in determining steam qualities at modterate to high pressures but only af quality values about 94% or reate. Ammonia and Retrigerant 12 Tables ‘Two other substances have property tables tha are listed in the appeni, Theve are ammonia and refrigerant 12 (R 12), dichlorodifluaromethane, Both are used ts refrigerants, especially R 12. Although its not necessary t Fepeat all the examples that ear be done with vhese tables, since tke techniques developed in using the steam. table are equally vali, itis worthshle to do some. The thermodynamic properties ‘ofammonia.arelistedin Tables A.8 and A, 10, andthe theemodvnamie properties of refrigerant 12 are listed in Tables A.11 and A.L2 fo SI. The Englis unit tables begin with Tables A.18 and A.19 for ammonia and Tables A.20 and A.21 for R12, Retiigerant 12 properties are also available in the TK Solver models R12SAT.TK and RIOSHT.TK, Example 4.6 Refrigerant |2jsused in retigeration unt. At one pointin the refrigeration proces, the refrigerant leaves the compressor at 12S psia and 1S0°F and enters the high: pressure tubing with alow rate af5lomv/min, Determine the velocity ofthe refi ‘ant in the tubing in feetninute ithe tubing diameter is in, Solution Given: R12 Dowsing through L-in.diameter tubing at cersin pressure and tem= perature and with a constant flow rate, Find: The velocity of the refrigerant in the tebing, ‘Sketch and Given Data: Bomtay é Figure 412ne Assumptions: ‘The flow is steady The state isan equilibrium state, allowing use of the property tables, Analysis: “There is no mention of energy in the prablem statement orin the infor ‘mation sought in the answers, so a frs-law analysis i not immediately indicated, ‘What relates the Now rate diameter, and velocity? The conservation of mass. TRUS, paw but poe and nate Nextdetermine the specific volume of R12. The R 12 issuperheated, because its temperature, 180°F, is greater dhan the saturation temperature at 125 psi, 97°F, Looking in the superheated tables yields a value of the specif volume of 40857 bm, Solving the conservation of mass equation for velocity and substituting in the variable values yields y= tit _ (5 Ibm/min\0.40857 Pflbmya ts in 2/82) a hin} 74.6 ymin Comment: While the conservation of energy is very important, many problems must use conservation of mass or other property relationships. In this problem, even ‘though velocity was aske for, information about kinetic energy doesnot provide the connection, Look for connections between the parameters given in the problem Statement to provide initial direction tothe problem analysis, = Example 4.5 In the evaporator ofa reftgeration system the cold refrigerant receives heat from the refrigerated space. The flow through a given evaporator is $0 Ibma/he, and the R 12 ‘enterstheevaporatorasa saturated liquid a¢~ 20°F and leavesthisconstent pressure process at +20°F. Determine the heat transfer during this process. Solution Given: eingerant ows though an evaporator at constant pressure, enteringasa saturated liquid and leaving asa superheated vapor. ‘Find: The heat transfer tothe refrigerant in this process. 468 TABLES OF THERMODYHAMC PROPERTI 119 ‘Sketch and Given Date: 1 ya20F penarh Figure 13 . Assumptions: 1, The flow is steady 2. There is no work crossing the control volume. 3. The changes in kinetic end potential energies are negligible, 4, States 1 and 2 are equilibrium states, so tbles of properties can be use. Analysis: This problem involves enetgy, so the irs-law analysis isan appropriate starting point OH m+ Ke + pely H+ rifh + ke. + pe lyy Employing the sssomptions yields 0 nigh, — hy) From Table 4.20 the entelpy for a saturated liquid at ~ = 42357 Bruton Since the pressure at state? isthe same asat state 1, and the pressure at stat | isthe saturated pressute corresponding toa temperature of ~20°F, 5.27 psa a= py 1827 prin Using the superheated tables, find the enthalpy Jng= 80.712 Bruflam Substituting inthe irslaw equation and solving forthe heat ransfer yields = ving ~ hy) = (50 Ibm ae ¥(80.712 ~ 4.236 Rta/tom) = 3823.8 Bruyhe Instead of the R12 property tables, the TK Solver models RI2SAT.TK and RI2SHT-TK can ve used {0 determine tne relngerant enthalpy. Simpy love RI2SAT-TK, change the units to English enter ~20 for Tet, and pres F9. Load RI2SHT-TK, change the units to English, enter the temperature and pressure, nd press F9.120° CHAPTER 4 / PROPERTIES OF PURE suasTaNCES Comment: 1 When a state js that of saturated liquid or vapor, knowing one additional conglton, suet as temperature, enables net determine al the properties at this state, 2. Often in open-system heat transfer problems, the assumption of a constant pressure process applicable = CONCEPT QUESTIONS ‘You are drinking ice water. I this pure substance! Explain ‘You are sinking ice ea with sugar added. Is tis a pure substance? Expin ‘What ete sierenc betas sturted and compressed guide? ‘What isthe dierence benscen superheated vapor and saturated vapor? Dring a heating process whe a liquid is oiling, the presure is increased. Will he temperature change of not? 6, What ithe diferensebstwssn he eric point and the tile poi? Can water vapor exit at =20°C? 8. Can liquid water exis at 0.08 psa? PROBLENS (5) 124 9, Inthe phase ranston process from compressed liquid 10 superheated vapor, what if fence do subsite and supereriial presures make? 10. Youare given a substances specific internal energy, specie volume, and prcsre. Can you determine is enthalpy? ‘What does fy meen physicals? Cen guy be expressed in erms of volume rather than mas? ‘What is quay? Where iit defined? Consider two cases of vaporization of a saturated lguid 1a saturated vapor cousin prosures of 100 KPa and S00 kPa, Which are equies move energy? 15, Consider two eases of vaporization ofa saturated liquid to a ssturated vapor acon temperatures of 100°C and 200°C. Which case regis more ene? 16, Without compresed guid tables, how would you determine the iqui's propesiesgiven its pressure and temperature? 17, How many independent properie arenes to define the state of@ pure subsiance? 18, Are liquid properties primarily dependent on temperature or on presure? 19. Why do foods cook faster in a presute cooker? 20, When a blockf dey ice, solid CO. spaced ona tables room temperature aed presse no liquids observed. Why? PROBLEMS (5!) 41. Aza tank continsa saturated vapor at 40°C. Determine he pressure and massa the ‘tank ithe substance i (a) steamy; (b) ammonia (2) R12 42 Determine for R 12 dhe flowing Ga) iT 85°C and p= 1000 kPa (exif A= 100 Kika and T=0°C. fo)wit T= 100°C and p= 800 kPa (a) pit T= 20°C and v™ 0.001 020 pg, 43. Complete the following table for ammonia, TO pita) 08) —hQU/Aa) w/a) v/a) Sate @ 10 1s) (50 700 © 7527980 f 12 1600 © 6 %0 i) 15543 €0 ‘olcae for eae sate whether ssubcoote ui, sturated igus mista, saturated ‘vapor or superheated vapor 44 Determine te volume occupied by 2 kg of sean at 1000 kPa and 500°C.cred ‘ewAPTEn 4 / PROPERTIES OF PURE SUBSTANCES 45 Complete the illowing tbe for wate, ka) sate Tee) rare) xt) NG/Aa) IVA) vA) re) 0000 3 00 38 os : ed 0 ® von 50 thetate of mast spr io masliqeld im the ering: (bythe Right ofthe guid-vapor 18 relfgeration system ses Ras the efeigecant. Thesytem evacuated, hen chargSd “The tank hs a volume of 0,5 m’, the liquid phase occupying 30% of y a pS aed nil eee ‘tm uncon suse seam a 300s Hen sane 417 Aor ibd KPa Deere athe eae (0) the al erent) the Seem de mesons 2 dasa 43 astberoatemaes sted mur ofecamandvat 300°C Deer) aaa ear toon acco esounccedbyh pe in nes use 1a ArigaeamontrniufenLOMPoisconied inane Het ded 414 te resus To 35 MPa ap the emperors fo 40°C. Deen he eat ane feel ois tt se at 04 Ma Ae the ono 9$85 te $15 Coin ea eresae nf 20 MPa ands temperature of 700" Determine the iti Meru lone othe se 46 Twotgeofanania st 0a an °C recoded ton presen 1 Trad Li There sna chang nine or tnt ney ar the die rosters gy 923 Determine (athe heat: (b) the work (cthechange i vlan) ee change in intemal ners 417 Tove kg of steam iitlly at 2.5 MPa anda temperature of 80°C have 2460 k oFheat ‘removed a constant temperature unl the quality is 90%, Determine (a) Pe oad oe irom: (0) presre when dry ssturated steam ens eh weak 448 You want 400 iter/min of water at 80°C, Cold nates avilable at 10°C and dry Saturated ar at 200 KP gael. They are to be mised crests Deseeie one and water flow cates requires) the pipe dizmeter, he vslosty i Wot tocaeeed 2m ‘419 Steam condensate ct 1.8 MPa leases a heat exchanges tp and ows at 3.8 isto at adjacent fash tank. Some of he condensate i ished ta slany ay fa SPA eae remaining condensate fs pumped back othe boiler. There's no subcoolne Decasaes (a) the condensate flow returned at 180 1Pa; (1) the steam flow predaens ar tas 420-4 chemical process requires 2000 kh of hot water a 85°C and {50 kPa Scan io available a 60 KPa ard 90% quality and wate avila cl) wa apace ahs Steam and water are mised in an adiabatic chamber, wth ihe hu weer eetinn Beton imine (a the sean flow rat: (bythe tans-line dare‘er ihe wont near oe 10 ms “421 The main stam curbing of ship is supplied by two steams generators, One generator ‘elves steam a1 60 MPa and 800°C, and the other dency seows ai SIP 530°C. Determine the team enthalpy and temperstire a the eaanee tothe ecb 4422 An adiabatic fe8 pump in a seam cycle delivers wate tothe steam gencraor a a temperature of 200°C and a pesure of 10 MPa. The water enter tomy ae 6 ‘stunted guid at 180°C. The power supplied othe pompis 7s kW. Detenhine the thas flow rat; (bj the volume ow rate leaving the putty (2) ke escent ose fhe exit conditions ae assumed to bea sifraed uid 2500" 423. o adiabatic igi ank hs two equa sevions of 50ers eerste by a prion, The fist setion consi seam a1 20 MPa and 95% gualiy. Tie ssond seine een Seam at 33 MPa and 380°C: Determine the eaulloium temperature aod pec ‘when the parton is removed “424 4 thong calorimets i ataced oa sen line where the seat empeatue reads 210°C. Inthe calorimeter the pressure 100 KPa andthe emperatans dee Bene ‘ine the quality oF he seam, using the team ble 4425 A throng alovimeterisconneciedoa mai tam ine where the pressures i780 kPa, ‘he calorimeter pressures 100 mmm Hg vacuum and 105°C Determine the act ual 4436 A pison-vlnder containing team at 700kPa and 250°C undergocsa constant gree roees uni the cuality is 708. Determine per kg (a) the Work done to) toe hese leaner: the change of ineralenery (the change of seabaine ‘427 Aneletriccalorimetersamplessiam withaline pressure of 0.175 MP. Thecalarineter cs 200 W of eleeiity to sampled star having a resultant pressure os 100 KES temperature of {40°C, and fow ro of 11 Sah Destine the main seas quale “428 Three kg ofammonia ate expanded tathermaly ina pson-stader ftom [0047s ond 80°C so 100 kPa, The heat losis 498 k/ka. Detetvine (a the stone ork foe ‘ange of enthalpy: (6) the change of intemal energy, “429 Refigeant 2iseagunded steadily nan isothermal process. The Dow aes 13.6ku/nin with am ink state of wer saturated vapor witha US quality ou alata oh14 CHAPTER 4 / PROPERTIES OF PURE SUBSTANCES 20a, The change of knetcenengyacros the devices 3S K/h, andthe eat desis 3181 RW, Determine the system power 430 4 tank conttins 0.2 kof a stamnonater minture at 100 KPa, Hea is added uni the Subeanse is seared sap at 1.0 MPa. Determine (a) the Tv diagram: () the heat ‘hed the tanks volume, 431 A pisomlinder contains R12 a saturated vapor at 100 KPa and compresses 29 (60) kPaana 40°C. Thework done i384) kp Determine the heat ns or gin in K/h, 4132 A pressure cooker hiss volume of ies and contains0.75 ke of water 3 20°C. The {ssecured and eat isaded, wih the airbeng vented i the process unt the resus 1200 ¥Pa, Determine the eat add and the final gua 423 Anadiabatic steam turbine receives kgsof team at LOMPaand 400°C, and the steaa ttt 50 kPa and 100% quality. Detersineaythe power produced: (5) the exit reat site exit oct 250 ms 1494 Plot the p- dagram for water on lotog coordinates fom the tripe pon to he cicl point, denoting the saturated guid and vapor vlc, The wait of prssoeiskPaand of $oecife volume ism /k8 {43 Plo the Pe ditram for water on log og cooadnats fom the triple point to the ciel fin, denoting the strated igi and vapor values. The unit oftemperatuteis "Cand Df specie volume is mg 436 Plotthe diagram for R12 on ineatog coordinates ftom ~ 80°C 1 12°C, denoting the saturated liquid and vapor values The unt of specie volume is ky. 437 serine te qoality of twophasermietare of(a) wazr at 180°C and aspecic volume (F015 mig (0) R12 a 745 kPa and specie volume of 0.020 m/s 4438 An R 12 tank basa volume of $4 lier and contains 3.6 kg. at L000 KPa, What i the temperature? 439 Determine te volume occupiod by 3 kgofwaterat 1000 kPaand remperatures of 100°C and 1000°C, 4440 Determine the volume ascupied by? keofsteim with quay 0f75%anda pressure of 500 HPs, 441 Reftgeraton abing is? em in diameter and 3 m ong and conains R12 a sturated vapor at tC, What isthe mas of R12 inthe Ying? 442 A plastic container holds 8 ites of water of 28°C, The pastel has amas of 50g ‘What the total weiht ofthe filed comsine? 443 4.0.5-n? tank contains ammonia ata temperature of °C anda quality of 8%, Deer- ‘ne the volume aceuped bythe var and bythe iquigand he perzetage of th total ‘volume each repeesent. 444 & 10-0 tank sued to hal highspresure stam fom a team generator ring emer ‘ency conditions when theturbine als. The atk contains steam a 500°C und 10 MPa ‘Thesteum cools until the temperature s 200°C, What the pressure and hos much, ny quid presenti he tank? 4.45 rigid tank contains 3 kao strated steam ata pessue of 3000 kPa Because of heat transfor othe surroundings, the pressure decreases 10 1000 kPa Determine the tank's ‘lume andthe quality of seam atthe nal tate 14.46 Steam iad ank sata pressure of MPs and atemperture of 400°C. Asaresultof heat rans, the temperature decreases tht othe suroundiags, 20°C. Determine) FROOLEMS (Eng Unis) 125 the tna pressure im kPa; (6) the percentage ofthe otal mss thai ai in he fina sate (2) the percentage of volume oecupied by the fg aid vapor a the nl ue 447 A 20-tertank contains a saturated ntingure of water and vapor at }00 kPa, The volume ‘occupied by th liquids 20cm. Heatisadded unt al thewaterewaportes an thea omians ony saturated vapor Determine the peste a is Sal ate 44.38 Water expands at consant temperature fom a saturated vapor at 250°C uni he specie volume i LO mag. Determine the final prestus, 4449 Two hg ofsteum i compressed at constant pressure in pston- 0, 51 WDEALGAS equamon oF STATE 139 esting in the following tim = R Risa common value foralltemperaturss, Additonal expsimensfordferet gases sont that ithe sre fr all pst, Thos i eal heuer gas eons “The constant Rhas a value of B= 8.3145 Kifkymol-K = 15 2 fub/pmolR = 1.986 Bru/pmol-R (5.8) Note that nd = 1 where isthe aumber of moles, and equation (5.3) becomes p= nk 63) Equations (5.1) and (5.2) ae the ones most ofien used, but equation (5.5) is used ‘when dealing with chemical reactions, The abbreviation keno! stands fo the molee lular weight expressed in Klograms: the abbreviation prio! stand for the molecular ‘weight expresed im pounds mas, Example 5.1 | Two kgofairat 280°K are contained in a0.2-m* tank, Consider the sito bean ideal | s2s, Determine the pressure, the numberof moles, and te speciic volume on « mass 1 and molal basis Solution Given: 2 kg ofa at 280°K and 0.2 m* Find: The pressure, moles, and specific volume on a mass and mole basis, ‘Sketch and Given Data: Assumption: The aris in an cquilbriue state. Analyst From Table A.1, R= 0.287 kifke-K and f= 28.97 ka/kpmol. Subst futing inthe ideal-ga law yields DIRT _ 2 k( 0.287 KI/hg-K) oy 2m) mm Oke At ~ GST Karke} 8O°K) _ 03.6 uPe = 01069 kermol132 (CHAPTER §/ DEAL AND ACTUAL GASES 2 02m) okey = Mo = (28.97 kp/kgmolN0.1 kg) = 2.897 m'/kgmol Ou mag Comments: 1. The ideal-gas law provides a simple mothod of determining ideal-gas state proper. tics, 2, Itisimporiant to he abe to conver fom the mass to the mole system, amt 5.2 NONIDEAL-GAS EQUATIONS OF STATE Tn actual gases the molecular collisions are inelastic; at high densities in particular there are intermolecular forces thatthe simplifed equations of state do not aocount for. There are many gas equations of state that attempt to corect forthe nonideal behavior of gases. The disadvantage ofall methods is thatthe equations are more complex and aqui the we of experimental coefficients, ‘One ef the equationsis the van der Waals equation o tae fora gas, which was developed in 1873 as an improvement on the ideal-gas law, The van der Waals ‘equation of sate is Rr_a 7 66) ‘The coefficients a and b compensate for the none characteristics ofthe gas. The constant accounts for the finite volume occupied by the gas molecules, and te a/S* term accounts for intermolecular forces. Constants for selected poses are giver int Table 5.1 {TABLE 51_vaN DER Waals constants Substance (eratmtfeomelt) 4?) aie 188) 0.0368 ‘Ammoaia (NH) 4a oom (Carbon dioxide (CO.) 3643 087 Carbon monoxide (CO) 163 0.0304 Helium He) Bat uns Hydrogen (Hh) oss Medhane (CH) bow ‘Nitrogea (N:) 3s Oxygen (03) agus 1 IDEALGAS EQUATION OF STATE 133, TARLE 5.2_CONSTANTS FOR THE BEATI-ORIOGENAN EQUATION OF STATE sobasnes a 2 % » te Me ess) 003931 Argon (40) 130780 cargos diate (CO) aria wim (He) 0.059 Hyceosen —o.008 8 o0s086 3625 Nitrogen N) Oxyge0 (03) the Beatte-Brid A second equation of state i fora gas Rni-e 7 sshere and the constants 4g, By. J, and are determined for individual gases Tale 52 ves these for certain gases ‘A simple but accurate 1wo-constant equation is that proposed by Redick and Kwong! in 1949: RY a FReFD The value ofthe constants «an b can be determined by noting shat the ist and second derivatives of pressure with espect to specific yolume atthe ritiel point are 2ero (refer 1 Figure 4.8) 0. Redchand NS. Kwong. “Oa he Thecmeyamic Solan, VAs Eguton ofa" Chem134 CHAPTER 5 / EAL AND ACTUAL GASES When these derivatives are taken, we find ‘This same approach can be applied tothe van der Waals equation. When the partial derivatives are taken, the following equations for the constants result: “These equations can be used 10 calculate the van der Waals constants rather than using tabulated values Virial Equation of State Gasequations of tate attempt to approximate the behavior of ges overawiderange ‘of conditions and thus become quite comples. An equation of state based on an init seis is called the viral equation of sate and iso he form +8), MD, ) v= F(1 os Te corfisens in apo (aed i cso nanos of ‘Doo Toco nd pent hope ge sBeSuulaly tog ised bane fea aceon ope Siete pteche rs te ved cece nih at saute seueSR ileal nrc comie sake mee ue Su ote dito Example 5.2 ‘Two kemolofairat 400°K iscontained ina 0.5 m= piston-eylinder A change of state ‘occurs, and the final pressures 15 MPa and the inal temperature 350°, Determine ‘the intial preerure and the Sal value oF specific volume, using the fdeal-pat Iw and the van der Waals equation of state 5: IOEALGAS EQUATION OF STATE 135, Solution Givens 2 kemol of aie initially st 400°K and 0.5 m? and finally at 15 mPa and 350°. Find: The initial pressure and the final specific volume using the ideal-gas and van der Waals equations of ate, ‘Sketch and Given Data: Fowess Assumption: Ai is in cquiibrium state italy and finally. Analysis: 20S m? n Tigmal = 0.25 m'ykgmol Find the values ofthe constants a and b from Table 5.1 a= 135.8 kPa (ekemol)? b= 0.0364 m?/kemal Substituting in the van der Waals equation of sate yields (6.3143 kiphemolKVA 4 (W25 miPAgmol ~ 0.0364 mrPkgniol) (0.28 m/kamod™ p= 134 MPa Using the ideal-tas equation of state yields p= 133 MPa136° CRAPTER S/iDEAL AND ACTUAL Gases For the final state, substitute into the ideal-zs law, yielding RY _ (8.3143 KY/kgmol-K)3S0°K) po (tS 000 KPa} 0,194 m/kgrnol Using the van der Waals equation of state requires a trial-and-error solution. This is easly done by TK Solver, The van des Waals equation isentered into the Rule Sheet, 4 guess value For spcitc volume i entered into the Input Colum of the Variable ‘Sheet. nv an iterative solution is invoked by pressing F9. | Comments Ax te inital state the difference between the values of pressure is only 0.7. Hence the ideal-gas law is accurate in predicting air behavior in many ine stances, except in thase cases of very high pressure and/or low tempersture. ea Compressibility Factor The Kdeat-gas law works well fc piesa low densities. As the presure ofthe gas is increased for a given temperature, the molecules are packed closer and closet to- tether, This brings about nonideal bohavior due co additional forees acting on the 5: IOEALGAS EQUATION oF state 137 Figure 55 Compresbity dissram fr nitrogen, ‘molecule. The other equations of state account for this deviation by introducing ‘empirical constants, The form of equation 5.2) is very convenient ta work with, and ‘4 method to account for nonideal-gas behavior using this form is availabe. If we ivide equation (5.2) by RT, it yields Pe. RF for an ideal gas. Ifthe gas is not ideal, this will equal some other number, Z; Bez “The symbol Zisthe compressibility factor. Is equal to one for an ideal gas, but wll havea value ther than one foran actual gas. Figure 5.5 illustrates how the compress ibility factor for nitrogen varies with pressuee along different isotherms. At room temperature, 300°K, the compressibility Fatoris unity up t0 7000 kPa. Note that as the temperature rises, it requires preter and greater pressures to cause nonideal-tas bbeiavior. In many application areas the temperature and pressure limits low us 0 se the idea-gus equation of state ve z Generalized Compressibility Factor Te form ofthe equation of state using the compressibility factr is simple. At this point the only dmicuty es in acquiring chars forall the gases, Fortunately ths task ray be reduced to that of developing only one chart This is accomplished by using reduced equations of state, The critical pressure4138. CHAPTER 5 /IDEAL AND ACTUAL GASES S51 IDEALGAS EQUATION OF STATE 138 1A generalized chart of compressibility factors for reduced temperatures asd ‘TABLE 5 CRIMCAL CONSTANTS pressures, Figure 5.6, was developed by Nelson and Obert, Tis may be used to find TABLE 5.3 CHINGAL CONSTANTS Maker Ten ag fe know the eit jes, The reduced volume, Vis substance weet RUM) oP Agron Beretta fe om ecient Theseus Vy aE Eo 8 air nor 376082 v_zRtp ‘Ammonia (9H) i703 «4055 «1128 —oaTze Vinge ‘anon (At) ou Isl 485 0074S cB RTIp. Be Ghonexce (Coy AOL. 3042239008483 by Netson and Obert? Gabon monodge(€O) 28011138380, 0.0930 Ethane (CH) hor oss 48880 lee (yE.) deoss Rd S222 Helv (He) 0038s 185 fxample 5.3 Honea i) lols 333M “Ammbaia is contained in a 2.0-m? tank at 2000 KPa and 160°C. Determine the Methane (CH) wos 9t«Met 982 ‘Specific volume of the ammonia using the generalized compressibility char, 2nd Methytalcobol(CH,OH) 320042 5132, 79S O18 ‘compere this value to shat found in Table A10. In addition determine the mas of itouen (2) Bos 162 3390899 ammonia contained in the tank. ‘onsen (03) mo sas 508 0.0780 Propane Sos) HO. 426 (O1998 water 0) Ios Gia 208 OSE sont =z, Owe olution Given: Ammonia is contained in 8 2.0-m tank at 2000 kPa and 160°C. temperature, and specific volume are unique a he critical point foreach gas. Table [Fists the ceticl properties of some substances. The reduced coordinates are ‘Reduced pressure p,~ p/fe, Where p, = cfitial pressure ‘Reduced temperature T,= 1/T, where T,= critical tersperature Redueed specific volume 2, 0/0, where = critical specific volume Find: The specific volume using the generalized compressibility chart and com- ‘pared to tabulated data, and the mas of ammonia in the tank. Sketch and Given Data: Powe. Assumptions: 1, The ammonia is a closed system. 2. The state isan equilibeium state, VLG Nelo dE. F, Ober, “Geoeral pT Properties of Gan" Tras. ASME, Oct. 154, 10st 1066 Figure 5.6 A generalized compressibility char.140. CHAPTER SEAL AND ACTUAL casts Analysis: From Table $.3 find the critical pressure and critical temperature of “ammonia, 11280 kPa and 405,3°K. The reduced pressure and temperature are rom Figure 56, the value of Zis 0.94, From Table A.1, R = 0.4882 ke, thus g RE_ OS4NO.4882 KI hee KI433°K) > (2000 N/m’) = 0.0993 mye This compares very well withthe value of specific volume found in Table A.10, 0.0999 mg. “The atass of ammonia inthe tank is Found from mo = Vs hus 2.0 my Ts wD = 20.18 ke Comments: 1, The absolute temperature and pressure must be used in calculating the reduced pressure and temperature values. 2, The compressibility factor is dimensionless. ss 3 SPECIFIC HEAT Specific Heat at Constant Volume Specific heat at constant volume, ,, is defined for any substance as 52 S0EORC MEAT 49 ro gue $8 Diagram ilsrating Joule ex- Figure $8 Pstonsslin arangements illustrating com sSntvalume and cossantpressore proces. periment regarding internal emery the internal energy change waszero, This ed tothe conclasion that speific internal energy is nota faction of volume for an ideal gas Mathematically, we may say that o-(2),4<(G) Since de> 0 from Joules experiment and the internal energy did not change, swe may conclude that «= u(7) only From the definition of spevfic hea at constant volume, equation (3.9) nel from the fact that the specific internal energy ofan ideal as is not a function of specie volume (Joule's experiment), the partial derivative in equation (5.0) becomes a total, derivative; hence du ar du=e,dT 6.10) a= me, dT on clue beating proces, 2sin Figure $a) te frst aw states 5Q~ 4+ aw142 CHAINER 5 /10EAL AND ACTUAL GASES va oe fi wats fim ova Geavemn- Th “The change of internal energy for an ideal gus is always denoted by equation (6.11), Tae process may be reversible, ireversible, constant-pressure, constant-vo- Tome, oF any other process. Ilernal energy, specific heat a constant volume, tem- perature, and mass are properties and do not depend on path. The equation of tate For internal energy, equation (5.11), follows from the defsition of specific heat at ‘constant volume Specific Heat at Constant Pressure ‘The coeficient isthe specific heat at constant pressure, and is rigorously defined as = (28) eek oat om utp From the definition of specific heat t constant pressure and from « + RT for an ideal gas, ah= car (25a) dH = mc, dT 6.150) ‘We now consider heat addition at constant pressure, as in Figure 5.9(b). Let us analyze the frstlaw equation for this system. 40 dU +p d¥= dU + dip¥) 6169) 8Q= dH forp=c «7 hence 8Q= dH = mc, aT 619) for ideal-ens constant pressure processes. 523 Storie HEAT 143 Foran ideal gas, the changes in internal energy and enthalpy depend only on the temperature; ifthe initial and final temperatuees are known, the enthalpy and inter- nal energy changes may be calculated. Thus, equations (S.iSa) and (S:11) are tue ‘only for deal gases, by the definitions of specific heat, We have therefore a method of calculating the internal energy and enthalpy for any process we know theend states ‘The work may be calculated if we know the process path, that is, ow the system changes state, Further Considerations ‘An important ratio that we shall use extensively is that of the specie heats, Ae oy Heretofore the specific heat has heen written ox a mass basis; it can also be ‘written on the mole basis ‘We denote the molal constant-volume specific heat as a(28)uneastk (upeote) ay ‘ak a-(22) ama (Gupeet) ay ‘The bar aver any property denotes that it ison the mole basis; ence both enthalpy, and internal energy, i, have units of klkgmol-K. The property on the mass basi is ‘multiplied by the substance’s molecular weight, Mf, 19 obtain the property on the mole bass, tha is, = Mth ‘Another relation between the specific heats and the eas constant may be devel- ‘oped by considering the enthalpy of an ideal gas. mute pow RT heuter ‘We now ifferentiate, and substitute equations (5.11) and(S.15a)intothe result ing equation 6.22) ‘Thuscyen though the specific heats may be a functisw of temperature for en ikea! gas tele diferonce i always constant ‘The specific heats in Table A.1 are measured experimentally. Specific heats may144 CHAPTER 5 /IOEAL AND ACTUAL Gasts be developed mathematically, but using experimental values adds to the accuracy ‘with which we may calculate, ang heace predict, system changes Tris interesting to not be eaining “caer.” Heat capacity was ‘one dare in temperature. To make heat eapa the system mas, sielding specie Heat capacity Variation of Specific Heat with Temperature Irmay have been inferred thatthe specifi heats are constant fo alltemperaturesofa tgs, This is not the case, The functional relationships denoting this variation are ‘etermine from experimental ess, Tale 5. lists several formulas that predict The sta given temperature. Figure $10 shows a diagram of the range under sonsderation, ofthe specific Beat equation for Table $.4 can be integrated associated with each bras eracures, This i Mstred in Figure 5,00 for water and carbon dioxide, where cere are more wibratianal modes available in the atomic stevcture than in the simpler diatomie molecules hydrogen specific heat of 3 specitic hess variation desired, an average value of spesitic heat can be with temperatre for five substances I inereased a set or the tempera specific heats vary with temperature because thee tional mode becomes greater, especially at high sem ‘and oxygen, Hence the specific heat vasiation is more pronounce. TABLE 54 FORMULAS FOR SPEGFIC HEAT VARIATION Wal TMPORATLURE ‘Sibrance Temperature ange (AS) ir 28O-1500°K ——O9N6T +2877 WT — 3974 WT Ammonia (NH) joo=1000° 1.81944 1936 ID-SP— 1789 x OTT? Sulturcionite 60.) 3O0=1000°K TEAR 0.7113 % 10-47 ~ 1.73 1047" Hydrogen Hh) 3OO-200K 119594 2.460 x 10 T+ 38ST Oxygen (0,) BO-200K S07 16T7T= + UILIT~ Navogen (, 300-S000¢K aS — 28797 + 5.35 x LOT Carbon monoxide (CO) 300-S00K ALS —T9T~P 94 Water (#.0) 300-3000°K 4613 — 109TH 96 Caibon dioxide (CO) HOO-3500°K—LS40— 4ST +413 x (OT Methase (CH) BOO=1500°K USNR ATL x 10-77 — 1429 10-47 Eniylene (CHL) 300-1500°K (4039 + 435% 1017 — 138 10-47 Ethane (CH) M1307 3064 SUI MIT— 133K 10-87 butane (Cabo) HOO-1300°R 3142 593% 10 T= 160 3 10-87? BOO-1500K ODL S48 WOT 167 x WT 1921 + 7.06 x 1O-4F— 3.73 10-7 Propane (CH Acetsiene (CH) ean (CH) thatthe idea of heat capacity developed from the days caloric theory of heat wasin vogue, A body, when heated, was considered 1 calorie necessary to raise the substance ity an intensive property, wedivie by Figure 5.10 The variation of constntresure Spectic heat wih temperature for four gases. Ploted from equations in Table 4, aed or hee fam, OF AN IDEAL GAS selves and with any surfce, 5:4 KINETIC THEORY —PRESSURE AND SPECFIC HEAT OF AN IDEAL CAS 145 Figure 5.11 Molecule A having elastic coision on sal 5.4 KINETIC THEORY —PRESSURE AND SPECIFIC HEAT “Thepresue tat ps rene cased by he impact of he ns molecules against 2 sure. Tie fies erete y the impacted othe change of moment es partileasithisandbounes fom tesurace.Kinetitheory olsun night inte How an ideal gas behaves We aut jvoke ¢vancy of aumptons, set whe ‘olume ofthe molecule snes, he ores beeen the molecuesare nelle, the molecules cn be ated tip spheres that have dst calison wh th ‘Consider molecule Ain Figure 5. J;ithasa incident velocity vq, and an angle of incidence ©,. The molecule rebounds trom the wall at an angle of incidence Oy where 6; = ©. Since the initial kinetic energy equals the final kintic energy, the hgolite value of the intial velocity must equal dhe aboolute value of the Asal velocity ql Iv] The velocity vector of the molecule changes because the ditec-146 QueTEN § DEAL AND ACTUAL GASES sion changes, but the magnitude ofthe velocity vectors the same, Thus. the change of ‘momentum for molecule A in the y direction is, 62) subscript From Newton’ssccond malay ~ Va)? Forany molecule thismay be writen without the lew dom, lr) oy a cugge of momentum. The ie fra molec 1 Equation (523) represents the change of een ch the oppnte walla distance Lay, and retary are 2Lhy ‘Substituting these values in equation (5.24) yields Fe mi/L Assuming that all the molecules have the same mass and summing over the total rurnber of molecules present, 2, yields Multiplying and dividing by 9 y Noting that ty in the y direction, we may whieh represents the average ofthe square of the velocity in they , {stermiae pressure ftom its definition of force per unitares, noting hat thearea i L 625) where 12 V; the volume containing N molecules. ‘Molecules are in random motion, 80 the pressure iss result of forces in the and 7 ditestions, Furthermore, because molecular motion is random, the kinetic ecies in cach dicecion must be the same, This has been experimentally verified, Thus and the magoitude of the ttal velocity vector for tne motecue ts WA BAA 54 INETC THEORY—PRESSURE AND SFEGIc HEAT OF AN IDEAL GAS 147 and the pressure may be writen as (5.26) Consier one mole of a substance; it wil havea volume and contain N, mole cules, where is Avogadro's number. Equation (5.26) becomes es a ander es ‘We have noted thatthe velocity vector has components in each direction whose average velocity isthe same. This is consistent with Boltzmann's principle of equ parition of energy, wherein the total translational kinetic energy has thnee equal ‘components(the kinticenergyin each direction). Thus the molecular mass has three degrees of freedom, f— 3, corresponding othe x, and z directions ‘The internal energy fora monatomic gasmolecule™ 3,isdescribedby equation (5.28) The equipantion principle may be generalized to include energy forms otdee than translational Kinetic energy, such as rotational an vibrational modes, In this ‘ase the internal energy may be written as 62 BE aff AL oral Since cyt 8 ru +92) so) For a monatomic zs such as lium, f 3. Substituting into equation (5.30) vields (p= ZOTH + 3/2) 5.1925 kl fea K ‘wich corresponds very well with the value found in Table (5.1954 4 ke-K). As ‘hestructure ofthe molecule becomes more complicated, however, even a diatomic ‘molecule such as hvrosen, H.ilustates te imitation ofthe kinetic theory moe! and the influence of other modes of eneray storage within the molecular structure Fora disiomic gasthere are three translational modes to rotational modes, and twv8 CHAPTER §/ DEAL AND ACTUAL GASES igure 5.12 Vacation of, of hyrogen with temperature. ibeational modes of energy storage, of degrees of freedom (f= 7), Thus for hydeo- Fea, y= 4125(1 + 7/2) = 18.56 KF /kgeK “which is much greater than the tabulated value of 14.31 KI /ks-K. igure 5.12 ilustzates the variation of specifi heat with teaperature for hydro sen, The molecule uses more modes of energy storage, exhibiting more Gesres of Fetdom, asthe temperature increases. Thus at low temperatures only translational Linoticenergy mode are used tostore nergy, whereasat high temperatures all modes are use 55 GAS TABLES ‘We have examined two methods of analyzing gxs behavior: the first i the use of an {deal ges equation of sate and the second is the use ofthe compressibility chart for feal-gas behavior, A third resource is available 1 vs, the gas tables by Keenan and Kaye. Tables A2—A are adapted from these gas tables, and Table A13 is an Abnadgement for air These tables account for the variation of specific heat with iEanperature for ial gas: Temperature i theindependent visable, nd abulated values for internal enersy and enthalpy are given on the same fine. Some other ssss tants 149 sob aa gen vals and we wil em sks them when ved Groep hai th vay is ah tot cnessat Note taons thing onan pes hs tothe issn subane ows gs wh vane pete hes The Sober model AIR.TK cortsnsnormaion ethan ininrmaton tain he ables a epee convnentdetemiaaton of the pes tmp, and spec “elu at ost pois an se changefntral eeray znd etal between Example 5.4 Air wth atemperatuce of 27°C receives heat at constant volume until the tempers ture is 927°C. Find the heat aed per kilogram using () specific heat from Table ‘As (b) specific heat using the equation fom Table 58 and an average temperature {6) the air table in Table A.2; (2) TK Solver model AIR. TK. ; Solution Given: ics heated at constant volume from 27°C 19 927°C Find: The heat added per Wilogear. ‘Sketch and Given Data: Assumptions: 1. The system is closed with no change in volume. 2. Tie inital and final states ure equilibrium states 3, There are no ehanges in kinetic and potential enerues Analysis: "The fs-law equation is ga Aut w 1 = 0 for constant volume, so @ (Case (a): For am ideal gas the equation for internal Aum (7; ~ 1)) = (0.7176 65 /kg-K)(1200 ~ 300K) 645.86 KI ks150. CHAPTERS /IDEAL AND ACTUAL GASES ‘Case (b): From Table 5.4, the specific heat at constant volume i = R= (09167 +2877 1O-AT = 3.974 X 10-47) ~ 0.287 018120019 sos 6, = 0.800 65 KI/keK = (0,800 65)(1200 ~ 300K) = 720.6 15 /kg Case (¢) From Table A.2, at 300°K, 1 = 214.09 1d fk; at 1200°K, v= 933.40 kg, thus, Au = 719.31 KI kg ‘Case (4); Using AIR. TK, enter the equation vi= v2 into the Rule Sheet and the two temperatures and an assumed initial pressure of 100 kPa into the Variable Sheet. Solve by pressing F9. FopectSS Seg Se, det dace) fae fee, Mabe) onperature, (ear deat, deat deat SRETHENSube tars aesraber abs (von s-Honte 2) Date “Wie. His Atel Lnatag sha yeay Bro/aiay Fats 18is? folag-e kuvony Owyhee, B/lir) Comments: 1. Because ofthe wide variation in specific heat over the range of temperature, using tic specific heat value rom Table A, results in significant era. 2, Using the air tables (Tables 8.2), the TK Solver model AIR.TK, or aspecitic heat from Table 5.4 based oan average temperature produces similar results. tam 55 cas TABLES 451 Example 55 Aptana contains 2K lin 200K an 100 KP, Th and 100s, The eto i coments ot" an 10 aetstasoestote Sunoundngainthe poe Deenc he al voluneand he wok done sn ering helium to be an ideal gas, cae “ Solution Given: Helium, an ideal gas, iscompressed irreversibly 7 a . ereversiby from 300° Kand 100 kPa to 450°K and 600 KPa. The process transfers 100 KJ af beat to the surroundings Find: The finsl volume and the work done in the process, ‘Sketch and Given Data: on aha Assumptions: 1. The helium is a closed system, 2. The initial and final states are equi 3. Helium may be considered an ide ges. ‘4. The changes in kinetic and potential energies are zero, Im states Analysis: The frst law fora closed system is o-aut apd +ap€ + ‘The changes in kinetic and potential energies are assume: Tee shang 8 14 to be zero. Solving forthe W=Q-av(CHAPTER §/IOEAL AND ACTUAL GASES Foran ideal gas the equation of state for internal encray is AU = me(Ty~ 7) = (2 baN3.1189 KT -KNASO"K ~ H00°K) AU'=935.7 kd Solving for work yields " 1035.7 kd 100 ky = 935.7 = “The minus sign on the answer indicates that work was added 10 the system “The idealaas law may be used to determine the final volume at state 2 ART _ (2 kgN2.077 13h KNASO"K) = 5 9 ys P (600 EN) Comments |. Te deal-gas law may be used to evaluate properties ata given state, regardless of Grete the system's proses i reaching that state i reversible or not. 2, Is important to remember the sign convention for heat and work. The fa nw is valid forall processes, hence the work may be determined from it for ireverible processes. The J p dV can be evaluated only for reversible pro- cases . |4, When a proces is irreversible, use a dashed line to indicate thatthe system's suceuison of states is not a succession of equilibrium states = J bxamnte 5.6 Fs ans comuln air a rent tempera and press and ae BT stapes ear aol ofa S00 ant 10 pana Belts J) 2 thm of air at 750°R and 50 psia. The valve is opened, and the pressure and ‘emt ah equi ves, Wot te) Sotution Given: Two adiabatic tanks contain air at diferent temperatures and pressures ‘Fhevalve connecting the tanks sopened, and the airreachesan equilibrium temper- ture and pressure, ‘Find: The final temperature and pressure ‘Sketch and Given Data Figure 5.15, S5.cas Tames 153 Assumptions: 1. The total amount of air can be considered a closed system, 2. The initial and final states are equilibrium staies, 3. Air may be modeled as an ideal gas. 44. There is no change in kinetic and potential ener. 5. There is no work done in the process, Analysis: The fs aw fora closed system, assuming no Work done and no change in potential or kinetic energy, is QR AU, + AU y= gel T,— T+ mee(T,— Te) Since the tanks ate adiabatic and considered ss one tank at the Anal state wit temperature The rt aw simply indicates that xe energy gained by one subsjstem is given up by the other subsystem. The mass for tank A may be found by sing the idea-gs law BV (000 Bein (149 in MEN3.RY) RT (5334 foftim-RYSOO"RY Suing nto the fist law uation, noting that Q= 0 snd the specie heats (.62)7;~ $00) = (2750-75) 7,=638.°R The final pressure may be determined from the ideatgas law, but fst we must ind the volume of tank B. RT _ (2 tomy 53.34 8 iIbm-RN7SO°R) fe Go ibhin N44 inh) vps iha ne “The ina resus aT CARTE 2 60.7 psia Comments: 1, If the variation in temperature within the system wer large, the assumption of ‘constant values fr specific heat would not he valid. The probiem could be solved using the tabulated values for internal energy, which account for variation in specifi heat wih tesiperatue 2, Use ofthe generalized compresibiity chart shows that 21 forall gas sates in {his problem; thus the usefulness of ideals equations of states @ good assump-154 CHAPTER'S /IOEAL AND ACTUAL Gases PROBLEMS (5) 155, CONCEPT QUESTIONS 45.11 Determine the specific volume ofthe following gases sing the generalized comprsibi fy emare 1. Why isthe term “specific nea” lsnomer 2. Upon what ieal-gs pres are internal energy and enthalpy dependent 3, How would you define an ideal as? 4, Cao actual or ideal gas avs be ued to predict nonesuiirium propery values! Why? ‘5, Are the specific heats oF an idea as constant? 6, What does the generalize compressibility factor indicate? 7. Why does the specific heat ofa gs vary with temperature? £8. Can theideals equation of tate be used a the ntl and Baal equibsium states or an ideal es undergine an imeversibe proses? PROBLEMS (51) 54. An unknown gs has @ mass of 1.5 kg and oecopias 28 m while a texiperature of 200"K and presse of 200 Ps, Determine the eal a5 constant forthe as 52. A motorist oaipsherautomobie tires with areiettype valve so that the pressurcinside their never wllexcoed 240 KPa gage), Shestartsasnp with apessure of 200 kPa (gave) nds temperature of23°C inthe ies: Durngthe long drive the termperatueof the arin the tives aches 83°C. Each ire contin 11 kp of sit Deterenine a) the mass of ir ‘Seapine each fre: (b) te peste of the ie when the temperature returns to 23°C. 53. A Gmtank contains helium a-10°K and is evacuate from almospheri pressure toa presi of 140m Fig vacuum, Determine (a he ass or helium remaining i the {ak (b) the mass of heim paraped out (6) The temperature ofthe remaining helium Tells to 10°C: What the presare n KPW? 54 A 1 Ske quantity ofethane cooled at constant pressure fot 170°C 1965°C. Deter ine () the change of ena: (b) he change OF inteoal energy che heat trans Fore) the work done 535 A Stank contains chlorine at 300 Paand 30°K afer kyofeorine hasbeen used Betermine the orignal mase and presse if the orginal temperature was 315°K, 156. Caton donde st 25°C and 101.3 KPa has 2 density of 1.799 kg/m, Determine (a) the ‘ss constant (b) the molecular weigh based a the gas constant ‘57 Given that cathon monoxide gus hasa temperature of S00’ Kanda speci volume of 14 ng, determine the pressure using the van der Waals equation of sate and the ideals equation of sate ‘58 Determine the specie volume of etium at 200 kPa sé 300°K using the van der Wass ‘uation of tate andthe idea gas equation of sae 59 Helin is assumed to obey the Beatie Bridgeman equation of sate. Determine the pressure fora teneratre of S00°C and a spose volume of 32 mig. Compa with fhe idealoge equation of ate 540 Given a pressure of $00 KPa and a ferperatue of $00°K for carbon diode, compute the spose volume using the Beti-Pridgemse and idea-as equations of sate {@) Meth alcohol a 6000 ks and 600°K. (0) Caron donde st 1S MPa and 300°C (6) Helio at 500 KPa nd 60°C. S42 Fora cera ideal as, the value of i 0.280 k1/op K and he Determine the values fc and $113 Fora certain ideal gas, 80.2004) ha-K and k= 1.25, Determine (a: (b) 30) M. S14 Fora ceria ideal as, ~ 11k /kgK and = 13, Determine fa) M(B) Ri) 5.18 The specie heat of caro dioxide may be found a Table $4 a5 funtion of tempera ture Find the change of enthalpy of carbon dioxide when it fermpertu is neresed fiom 325°K to L100°K, Compare this valve with tat calelated for constant speci eat found in Table A. {16 A mountain sto be measured by ings change in presture at constant teperatue ‘A barometr atte base of he mountain reads 730 nm Hg hie the top it reads 470 mmm Hg. ‘The local gravitational acceleration ic 9.6 m/s-® Find the moutai's heat, Assume T= 298" 5.17 Anempty. opened ean s 30cm high witha 10cm diameter. The ssa, withthe open end dow, spushed underwater with adensityof 1000 ken Find the waterleveliathecan when the top of the canis $0 cmt helow the surface. Thera equilib exits at lh je of kis LTS $18 Compute the average specific hest at constant pressure using the equation found in Table $4 between temperature limits of 380°K and 1200°K for) ntogen (b) meth ane; (6) propane 549 Deteresine the specie heats, cond, of seam at 7 MPa and 500°C, Compare histo the speci heats calulated st? MPa and 350°C $520 An nsuste, constant volume system containing 36 ky of receives 534d of pale ‘work. The inital tempereuze i 27°C. Determing (al the fa empersture; (0) the ‘change of internal eney 521 A toy gieous system in a plston-clinder revives heat ate consent pressure of 3804Ps. Theinternal energy ineweses 300 J and thetemperaue ineeates10°K. ahs ork done is 1001, determine (a) (8) the change in volume {5.22 Using Table A.2 calulate the specific heats. constant pressure and constant volume for ale at1000°K. (in Use «y= MAyAT) 23 A spercal balloon measures 10m in diameter and Bled with eum a 101 KPa and 325°K The balloon is surrounded by aia 10) KPa und 320°K. Determine the iting Toe ‘5.24 Repeat Problem 5.23, except that now the balloon consis hyogen. Note that the molecular weight hydrogens oneal ba of hele Does this ale the iin forse! Why? 15.28 Desermine the size ofa spria ballon requires to lit payload of 136k Thegasto be wed is helium at (01:3 KPa and 23°C, The surounding air 101.3 8Pa and 10°C 5.20 A trogen cylinder ot. m orginally nasa presite 17.25 MPsando temperatures! 20°C. The nitrogen i peadually usd uni he presuce 2.98 MP, the tempers femainingat20°C. What isthe mass of strogon ued? Ur the compress chart and Ideal as kw and compare rel,‘CHAPTER § /OEAL AND ACTUAL GASES 1527 A.notirballoonist wishes to operate at anal where the prsure 6 94 KPa andthe temperature ie 274°K, The ballon diameter i 10m, andthe payload s 200 ky. Whst temperature most the arin the balloon be to ahiee this? 1.28 A 0)-m* seu tank hold aie st 20 MPa and 10*C. Ata depth of 100 en in water (p= {000 gies?) diver uses G4 m/min of ata» pressre equal co that ofthe water sorroupding her. ASume the temperature f he alr remains at 10°C. Determiae the time until he ai consumed 15.29 Given the equation pe RT, show that he fellowing equations may be derived fhm it (PP = MRT.) pV™ ART (6) pom RT dh pe = RTM 5.30 A weather ballon is 3m in diameter and contains helium at 27°Cand 104 KPa, The balloon ss to an altitude where the temperture is 17°C and the pressure is 1S KPa Calculate the mass ofhelism inthe balloon ad the change o balloon volume at he high alte. 5.3 Ag 0m tank contains 40 ksmol fan del gs a S0°C with a molecular weight of 25 g/kg. (a) Determine the gas pressure (b) eat ransir occurs andthe emer tore dereses 20°C. What she prose? o-m*tank contains .Okgmol ofan ideal sat 400 kPa witha molecular weight oft ‘Ke/kemol. a) Determine the gas temperature (b) Gas is emoved from the nk, tm porture remaining constant, unl the pressure decreases to 100 KPa, What ms of gs tras removed ‘53 A topieal adult breathes 0S liners oie wih ac breath and has 25 breaths per aut ‘Ac 101.3 KPa and 22°C, determine the mass ofr per hour entering a person's lungs. This person now is aking ona mountain where te air ie—10"C and the presse is 89 kPa. How many breaths per minute are required ifthe mass of ai per hour entering the lungs isto be constant? ‘SM Dstemnine the compresiilityfictorfor water vaporat MPa and00°K using) ata ftom the generalized compressibility char: (b) data from te steam tables, ‘538 Dstermie the pressure range forairin ka foe 0.98 < Z-< 1.0 aemperatores 02 BT,, and 7, Where 7-5 the ential temperature 1536 Tae same as Problem 5.35 exept the ga it ago, ‘5.37 An adiabatic tank as an internal partion tha separates to gases, On on si ofthe Pariionfair— 1.5 kaa S00 KPa and 350°Kzon te other idee ammonia 30 kg at 500 MPa and SO0°K magne now thatthe partion i ree 10 move and allows the conduction of heat fram onesie to the other. Determine the fil temperature and pressure of each gs, essuming thatthe ideals laws, constant specie heats, may Be teed 5.38 Two wel-insulate tanks contain sat dierent conditions. Tank | contains? kpofaie 21 800°K and tank 2 contains ig ofairatan usknown temperature A vale inthe ine ‘connecting he tanks is opened, andthe equilibrium temperate found to be 600°K, Determine te intel temperature of the arin tank 2 5.39 air expands in a piston-stnder fom 200 KPa, 0.2m, and 300°K toa final tate of| (04m and 400°K. The presture vais easy with Yolume during the proces, Deter ‘mine the ou abd the het traf 531 FROMLEMS frgien Unts) 187 PROBLEMS (English Units) “51. Determine the change of enthalpy forair and fr carbon dioxide when the temperature ‘changes fom 70°F to 1000°F. Use equations fom Table 55 +52 Onelbm of airs heated in a 0.5-4 tank fom 70°F to 200°F. Detzesine (a the heat reat () the ial pressure, *523 Ammonia hasa specific volume of 1496 at 30 aia and 300°F,Deteratne the specie alum, using he iealzs a ai the compress acon +504 An del gas with molecular weight of4S expands at constant presuse om 150°F a 30°F. During the process 50 Bu areadded to he gis, whose mas 0.2 Tom. Deter imine and *S$_ Carbon dioxide at 937°R and 14.7 pia has a density of 0.1123 Ibm Determine (a) the as constant (b) the molecular weight based the 2 consan Foracerain ideal gas, R = 43.0 febfom-R and & = 1.25, Determine (a 6,6 WF *5:7 Foracensin ideal ga. 255 Bulb and = 13. Determine (2) (0) 6) *58 Determine the specific heats cj and cof stam et 1000 psia and 90°F. Compare to specie heats calculate st 1000 pia and 62" F *59 A mountain ic measured by nding tbe change in prasure at constant temperature. A barometer the base of the mountain eas 28, 74in. wile at thetopit eas 19.14 in He, The average local gravitational acceleration 31.3 ee. Determine he height afte temperature may be astumed constant at 70°F 5.10 An empty, opened can is 10 neh and $ in in ameter, The can, wit he open end down, i pushed under war witha density of 624 Ib, Find the mate evel nthe fan when the fon othe can | TMbeow the surfs, Thermal ester cia all *S: A 5004 tankcontains chlorine t720°R andatmospherc pressure, hisevaceatedtoa pressure of 29 in. Hg vacuum: Determine the mass ofch erie pumped oto te atk, "5.2 An oxygen elinde of 1 originally has a presse of 1000 psa anda tempertur of {60°F The oxygen is pradully used unl he pressure i400 pa teperatne roma ng constant. What mass of oxygen is used? 5.13 An unknown gas hasa massof 3.3 bm and occupies 25 while 80°R and 30s Determine the ps constant. *5.14 An insulted, constantvolumessstem containing 3 thm fac reveives 39,000 bref dale work. The initial temperatore 85°F, Determine te change f interna ners bfthesystem an the ars nal tempersture *548 A piston-ylindercomains2 Ibm ofa gasand reeivesheaetaconstat pressure of 85 psa. The ntral ener inceasesby 40 Btu and the temperature nce: Oy 120" [fhe work done's 120 Bt, determine he specie hea coestant pressure fr: gas apd ine changein volume of stem *8.6 4 woather balloon i 10 fin dsmeterand consis elim a 7°F aad 14.7 pi. The ‘alaon rises 19 an aude where the temperate i Fred the pressure is 2.2 ps188 CHAPTER $ /EAL AND ACTUAL Gases Calcite the nas of hatin inthe alloon and the change f balloon volume athe high altitude 95,17 Arg 4.8? tank contains 30 pmol of an ideal gas at 120°F witha molecular weight of 24'bm pmol) Determine te pas peste. (2) Heat arse occurs, and the wep sure decreases oUF: What ithe presse? *5.8 A SOs? tank contains |-pml fan ea gas 895 pia with amolocuar weight of 31 Tm/peol. (a) Determine the gas temperature. (b} Gas is removed from the tak, temperature remaisiog constant, util the pressure decreases to .7psia, What mass of pastas removed? ¥5,9 Atypical adult breathes 20in2 of air with each breath and bas? breaths per minute. At 11.7 pia and 70°F, determine the mas of at per hou entering person’ uns. This pers now iskiing one mountain where the iri 10°F andthe pressures. pi, How many breaths perminuteareroguzed ifthe mass of arper nou entering the Ungs ieto be constant? *5.20 Determine the compressibiliy factor for water ¥apor at 200 psia and 1000"F using (a) ‘aia fom the generalized compress cht (9 ala fom the star able, #5,21 Determine the resune ange or sirin pia for 0.95 < Z-< L.0Sat temperatures fT, BT and 47, where T, te tical temperate +522 The same as Problem 5.21 excep the gs is chlorine +5.23 An adlubatc tank has an internal partition that separates two 2356 On one side ofthe partion fair——3.3 hm at 78 pia and 170°F,on he othe side's smmonia—6.6 bmn 120 pss and 40" Imagine now thatthe parton i rete move and allows the ‘ondvetion of het (em obe side to the ote. Determine the final tempeeture and peessue ofeach gas, assuring thatthe idea-gas ls, consant specie heats, may be tre +5.24 Two wellinuulated tanks contin air at diferent conditions. Tank I contains 4m of| seat 440°, ac tank 2 contain 2 thm of ira an unknown temperature, Avalvein thelne connecting he weksis opened and the equiiur temperatures found tobe $O80°R. Determine the initial temperature ofthe sii ok 2 +525 Airexpandsin apistonlinder fom 30 psi, 20, and S40°R roa final stateof4.0.8 land 720°R. The prestoe varies inesry wih volume during hs process. Determine the work and the eat tater. COMPUTER PROBLEMS (C51 Compute the reste of ara a temperature af {00°C and 2 specie volume of 0.2 1m), using (a the ial zs law) the van dee Waalsequation;() the Beatie Bridge tan equation f) te Redlich Kwong equation, (€52 Solve Problem 5. using TK Solver, (C53 Solve Problem 5.10 wsing TK Solve. (3.4 Compute the space volume of iat 5 MPa and 200°. usng(a the dea asa) thea der Wes equation: (the Beatie Srieman equation; (tne Redih-Kwome eowation CONBUTER PROBLEMS 159 (C55 Compute he compresibity factor or nitrogen sing the Redlch- Kwong equation for temperatures of 300°K and 150°K and a fang of presses between JOD kPa and BMPs, Plot the resus and compare them to Figure 35. (C56 Compote the specifi volume of superbeate scam using the ieal-gs athe van det ‘Wass equation, and the Relich-Kwong equation for (a) 10 MPa and 380°C. (©) 100 kPa and 150°C fe) Compare the ress to the iebulted vanes inthe team tables 52 Compute the ining force of a heiumflled balloon from sox level wo am altitude of 10,000 in increments of $0 Assume atmospheric prssre and temperature vary Tinea from 14.7 psi and 60°F at sea level to 10.1 psi and 80°F at 1.000 The balloon basa diameter of 90, and ils presi and temperature ae equlibriam with the serounding a. AS the balloon ses, exces elms vented to the amosphere (C58 Compurca table of theiereral energy and enthalpy of irasa function of temperature from 300°K to 1500"K. Use the equation for specific heat variation in Table Assume the enthapy is 300 LI/kg and the ternal ener is 214 Wk at 330°K. (C59 Using the equations in Table 54, compute and plot curves of specie heat rato Uk) ‘versus temperature in the range of 300°K to 1500°K fer (a) metnan; (8) thane (6)Energy Analysis of Open and Closed Systems [At this point you have the knowledge and the techniques 1o undertake a variety of| ‘energy analyses fora variety of open and closed systems undergoing reversible ot irreversible energy transfers. Indust plants ae designed in part by combining individual thermodynamic processes; a thermodynamic analysis typically recedes ‘the mechanical design, an analysis ofthe ype that you can gin, tn thischapter you will 1 Further understand equiltvivm a « Lovestigateconstant-praperty processes for open and close systems + Consider generalized rversible proceses «Explore transient analysis of open systems; + Develop a greater understanding of processes combined to form cycles «Extend your perceptions of energy applications and conservation, nomeguilibriam process; 6.1 EQUILIBRIUM AND NONEQUILIBRIUM PROCESSES: 160 ‘We know thata process occurs whenever a system changes from one state to another sate. Nouldbe convene ite a nev te ph hs pres allows. Howe, 85 soon as the process path is mentioned, an equilibrium of reversible process assumed to occ The eslibriam surface uirted it Figure 6.1 shows tne pat oF 164 EQULUBRUM AND NONEOLILCRUM PROCESSES 161 gue 641 Projection of an equilbrura Foyt ste path on a>) pane the process from state | to state 2. Imagine that a light is shown on the surface; 8 shadow, or projection, ofthe path wil be made on the plane surface, This is denoted by the soliline on the pV plane. Oftena two-dimensional surface is used in drawing system path. Itmay be helpful, however, to remember how this projection accurs; 3 projection of an equilibrium process is implied 2s soon asa continuous function is cava, ‘What ifthe process were an irreversible one going again between sates t and 2? Let usastume thatasitecossesthe surfacein Figare6.1,adotismarkedon the surlace ofeach crossing. Figure 6.2 raght denote such a process, with its projection on the PY plane. From mathematics we know that a dotted line is a discontinuous function. To find work, we must be able to integrate p dY along a continuous path from state {to state 2. Hence, when the pracess is irreversible, the peth is discontinuous, and we ‘cannot integrate to find the work; the work must be found from frstlaw analysis in these cases, 5 oure 6.2 Proiecion ofa discontinuous, Steisriom rice reversible, ptt ona pV plane162 CHAPTER 6 /ENERGY ANALYSIS OF OPEN AND CLOSED SysTEME 6.2 CLOSED SYSTEMS Constant-Pressure Process Science evolvesby taking individual cases and relating their common aspeetsto form 44 general case, The temptation isto present the general case and assunte the special ‘cases willbe understood. However, experience indicates that people grasp the more complex or general case when they frst understand the simpler cases, Before we proceed in solving some problems, we must frst decide whether an ‘pens or closed-system analysis iso be used Although here the sample problems and discussion will indicate the system classification, in homework problems and in real-worid situations you must decide. ‘We consider irsta constant-pressure process fra closed system, illustrated in Figure 6a). The system receives an amount of heat Q, performs work Hand experiences changes in internal energy, AU’ © ~ Uj. The fist law of thermodynamics for 2 lose systera at rest, vali forall proceses is O=(~ Ut ey For seversible processes we may write the fst law as Figure 63 (a) A consancpressure process with beat accion. (b) Graphical interpretation of meckanial work fora consantpeesue 6.2 cose systems 462 5Q=dU+pdv (62) Also, H=vsp) alt= dU'+ pdV'+¥ de (63) p= 0 forp=C 8Q=aH torr 64) Foran ideal gas with constant speci heats, AH = mefT,—T) I (659) AU= me4T;— 7) (6.58) For pure substances, the values of enthalpy and internal enenay may be looked up in tables Fora reversible constant-pressure process in a closed ssstom, the wark is we | pav=puz-V) [iran e We phn Using he ideal as equation of state, p= RT, ves u mR(T,—T)) 5) Examining the system in Figure 6.Xa) more closely, we mote that when the piston expands, itdoes work against the surroundings, displacing them aswell as delivering ‘dgitional or net work available for other purposes. Very often the surroundings” pressure is simply atmospheric pressure, The work expended in displacing the surroundings, Her 58 Wan | paw * Pan 02 Vi) en ‘Does the work agains the surrounding’ pressure dependl on the system process? No, This pressure is almost alvays constant, atmospheric presure, so the work against the Surroundings isa function ofthe initial and final system volume, “Thus we may find the system work from the frstlaw analysis ofthe system, but to find the net work available fo nun a piece of equipment, we must subtract the work saainst the surroundings from the system work w - 0 Fa 6a) ‘The net work does not influence the system work, It provides us with additional information, but in most problems we are interested only in system work,468 (CHAPTER 6 / ENERGY ANALYSIS OF OPEN AND CLOSED SYSTEMS Example 6.1 A piston-ylinder containing ar expands at a constant pressure of 150 KPa from a ‘temperature of 285°K 10a temperature of $30°K, The mass of airin the eylinder is 0.05 kg. Determine the system heat and work for the process as well a the net work availabe ite surroundings’ pressure acting on the piston is 101.3 KPa, Solution Given: d eslinder containing air expands at constant pressure from an initial state ora final stale, The states are spociied, as is the surroundings’ pressure, Find: The system heat and work and the net work available Sketch and Given Date Bowey Figure 64 Assumptions: 1. The proces is constant-pressure and reversible 2. The changes in kinetic and potential energies may be neglected 3. This isa closed system, 4. Air isan ideal gs. Analysis: Fora closed system undergoing a constant-pressure process the ist law tmay be reduced as follows 80~dU + nav 8Q= dll V dp ap=0 6Q~ att onan 52 closen systeas 165 Air isan ide! gas atthe temperature and pressures inthis problem, thus AIF = me, AT = (0.05 kg)(1.0047 Ki/kg-KYS50 —285°K) aH= 133K From the fist law fora closed system, Q'= AU + I", we note that by finding the ‘change in internal enctgy for ait, the work may be determined AU me, AT = (0.08 kg)(0.7176 KI/kg-KX530 — 285°K) aU=95k Substituting in the fist aw yields We Q-a=133-95 sk ‘This isthe work thatthe system did in moving the piston from sate | costate2,Some ofthis work is not available fora useful purpose, however, but must be expended in displacing the surroundings. The work zgainst the surzoundigs is found from equ tion (67) Wag = Pau 13 8 From the idel-gas equation of state = mRT 1D, = (0.05 k3V0.287 ki /kg-KX28S°K/(150 kPa) 0.0273 m mT ip (0.08 kgX0.287 ky /ka-KXS50°KY(150 kPa) Vs 6.0526 m? Wg = (101.3 KPAKO.0526 ~ 0.0273 mv?) = 2.56 Kd wa = 38 2.56~ 1.23 1 Wag = Wg Comments: 1. There are ather ways to solve forthe system work. integeating pd for insane Regardless ofthe methodology. the results will be the same. 2, Thework aginst the surroundings can alwaysbe determined usingexvation| 6.7), whether the process the system undergoes is reversible or not 3. The heat transfer is equal to the change of system enthalpy only for reversible constant pressure processes. 2 Example 6.2 A rigid I-m? tank receives 500 Ky of heat and paddle work delivered for 1 with a shaft torque of 1 J and a speed of 300 rpm. The tank contains steam insialy at 300 kPa and 90% quality. Determine the final system temoerature Solutiow Given: Atank contains wet steam and receives heat and paddle work increasing the system's enerpy166 CHAPTER 6 / EXERGY AALYSS OF OPEN AND CLOSED SYSTEMS 62 costo systevs 467 Find: ‘The final sytera temperature | heat into a sytem is postive, yields Sketch and Given Dat 500 = AU = 113.01 613.1 KI= mig ~ :) = (1.833 belay ~ 2345.8 IA) 2580.0 keg In this situation we know the final states defined by its inernal energy and specific volume, = 2, fora constant-volume proces From the superheated steam table we find that the final state's temperature is approximately 220°C. Thisis found by performing a double interpolation matching ime both the specific volume and internal cnergy, a tedious manual task, but one readily sccomplished by TK Solves, SATSTM.TK compute: a temperature of 221 "Cat restate of 410.8 KP Comments: ‘ewes 1, Paddle work is always negative and irreversible: it can only be added to the system, hence negative and the sytem cannot cause the pal to rolae, hence ireves- ib Assumptions: 2. Double interpolations in the steam table are quite time-consuming when done {, The sytem is constant volume and dose | ‘manually. Solution on the compute is much easier and faster, 2. The vstem mechanical work is zero in light of assumption L 5, Mechanical work fora constamtvolume process i ef earls of any other 3. The inital an fina states ae equitriom sates energy interactions = 44 The changes in kinetic sn potential energies a zo. Analysis: ‘The first law for a closed system, invoking assumptions 2 and 4, may be Constant-Temperature Processes “= switen as | “The thind type ofspeca process we can envision sa reversible constant temperature - process. Because an ideal-gas equation of state is used in this discussion, the results i aeunlla) ‘ust be limited to ideal gases. tis, of course, possible to have constant-temperature where 1, sth pate work added tothe system by the rotating propeller, processes using table of propertics, butte folowing equations do n0t app ‘The “properties of steam at state I are found by sing Table A, ‘Consider again a piston-elinder in Figute 6.6), which eecives heat and ex vielding 1 = H+ Xi 560.9 + (0,90K1982.9) = 23 y+ xg = 0.001 073 + (0.903.606 78) 2, = (1 m®)(0.5454 ens) ~ 1.833 ke Skike 5454 mpg 4 ‘The paddle work may be found from equation (3.20), Wi, = to = (1.0 J/radX ews} rade BY3600 5/5) W,= 113 1005113. Substituting nto the frst-law equation, noting tht work ntoa system is nepativeand met Fou 6. A consantiemperaure proces in a piston- i) “Taking las of both sides and solving for nviekds n= 1259 ‘The work may be evaluated from equation (6.195). qu PRET) _ (0.1 gy .077 ae KE38— 275K) _ I-n (1 1.259) ~ = 145680 “The heat may be found by substituting into the firstlaw equation = 56.6~ 145.6~-89.0KI “This problem can be easly solved using TK Solver. The basic relationships ofthe polytropic equation, the ideal gaslw, the fist law, and polytropic work fora closed system, are entered in the Rule Shect. Entering the input values anda gues value for ‘nin the Variable Sheet produces the following resultswea “CHAPTER € / ENERGY ANALYSS OF OPEN AND CLOSED SHSTENS Comments: “The negative sign shows that work was done on the helium, compressing it “The negative sign shows that heat was rejected from the system, ‘The enersytermsingicate that work was daneon the gas some oftheenergy raised the helium’s internal eneegs. and the remainder was rejected as heat 10 the surroundings. " Example 6.7 ‘Aturbine receives 180 Ibmysec ofairat 63 psia and 2450°Rend expandsit polytropi- tally to 147 psi. The exponent 1 is equal to 145 for the process. Determine the power and heat fx, Solution Given: surbine seceives aie and expands it between two states potytropicaly Finds The beat and work foxes aeross the conteol volume. Sketch and Given Data Figure 6.36 Assumptions 1, Airmay be considered an ideal gas with constant specific heats, 2, The polytropic proces is reversible 3, The changes in kinetic and potemil enetges may be neglected 44. The sir lows steadily through the turbioe, The fest law for an open, steady-flow system is Analysis: 0+ ny + (key + eped] = + Hilly + keds + (res) “55 Twmesomacess CvCLES 195 ‘The power may be evaluated from equation (6.23) on" sr= ({s) estoy. orem R280 as [23 i= 29,499 Buu/see = 37,492 bp ‘The change of enthalpy for an ideal eas is (y= mye 1) “The final temperature may be found ftom equation (6.184). 7 “The heat ux, subject to assumptions, is O= ry hy + 130 Tom/see}0.24 Buuslbm-R](1560-~ 2480°R) + 29,499 Btu/ser O=—2541 Brujsee Comment: The negative sign on the heat transfer indicates that itis leaving the control volume, = 6.5 THREE-PROCESS CYCLES By combining two or more processes it is possible to construct a cyee. In later chapters we will analyze several applications ofeycles, but for now let us consider ‘hee processes, joined together, forming a cycle. Three is che minimum number of processes to create a practical cycle. In Chapter 3 we noted some interesting behavior for eyeles, namely, that £40 = 94 or 30 = 2H. With this in mind, let usconsidet the following example,CHAPTER €/ ENERGY ANALYSS OF OFEN AND CLOSED SYSTEMS Example 6.6 ‘A iree-process cycle uses 3 kg of air and undergoes the Following processes: poly- {opie compression from state 1 to state 2, where p, = 150 kPa, 7, = 360°K, p, 750 kPa, and n= |.2;constant-pressure cooling from state 2rostate 3; and constant- temperature heating from state 3 to state 1, completing the eyele, Find the temperatures, pressure, and volumes at each state and determine the process and eyele heat and work. Solution Givens» thrve-process cycle using air, with details of the various processes that ‘constitute the eyele Find: The temperate, presure, and volume foreach statei the cycleand the heat and work for each process aswell asthe net Rest and work for the eye ‘Sketch and Given Daves Assumptions: 1, Air behaves as an ideal gas with constant specific heats 2, The processes are reversible, 53, The changes in kinetic and potential energies may be neglected, Analysis: Thekey o solving three-pracess-cycle problemsisto draw asketch, Once that is done, follow the processes around the eye State 1 4 = AT 6.0 ba0.287 eee i Process 1-2, pV" = a ark (3.0 ky0.287 ke/kg-KA70.7°K) 730 KPa 0.840 m Process 2-3, p= Cand Ty= T,= 360°K, since the process 3-1 is ata constant temperatuze! y= TEh ogi m T= 360K At his point let us calculate @ and J foreach process. QU Ut Ms T-T) 5 W yan RBA T = —a76.5 13 me Ty~T,) = 238,31 = -2382 KI ay Hy Hy mel ~ T Os3= GU + Woy Uy = Uy= me(Ty— 7) =- 2383.3 W,=-95.3 kd “The work could also be evaluated by Jp d¥. For corstanttemperatuce processes, = stn (22) emai) Os Os. = Wh = (8.0 kgH0.287 KI/Ke-K360°K) In 2OW-128k) BH'=—2BKI Comments: 1. The net work is equal to the net heat. 2. The eylic work is negative, indicating thatthe eye equites a net work input 10 operate 6.6 TRANSIENT FLOW ‘The typical situations studied in undergraduate thermodynamics are closed systems and steady-state open systems, However, the unsteady open ssstem mist be consic- ein transient flow: the two cases that we will consider arechargingand discharging ack. ‘Consider equation (342), which may be rewritten es deyns9— (14 S40) dign (ne ee188 (CHAPTER 6 / ENERGY ANALYSS OF OPEN ANO CLOSED SysTEMS Figure 6.18 Shot for charging and tcarging a nk where for any instant of tim: quation (6.24) may be integrated over the control volume yielding asnonws | (toZ4e) sme (v4%+2), tne 629 Furthermore, the change of energy within the control volume is equal tothe change of internal energy. Thus, equations (6.24) and (6.25) become dtgnsgmor +(e mvs +42), dng= (rE +2) ane 625 AU a-ws | (tee) ame f(r ee), mw can Discharging a Tank ‘Consider Figure 6.18, which lustratesa tank connected toa supply lin. The volume ‘of the connection is considered negligible. Apply the frst lst the contol volume {equation [6.26 ay s+ (i+ Sree) tee (628) Note that '~0 and dmg ~ 0, Furthermore est he veloc ofthe et $Secatoleswthan 3 athe change otto besmal Thus netics penta Shengs may benepecee. Thi td Ag = 60+ (drag (629) “The typical assumption at this point is that the tank isadiabati: itis not, 62 must be evaluated by other means (heat-transfe analysis, experimental data) ‘Thus, for 44Q= 0, equation (6.29) becomes 630) Se TRANSIENT LOW 138 However, dtm) = u don + m di, and upon substituting jaro equation (6.30), us din-+ mn du h dm dma mae Forany substance, b= w+ pr hence am _ du mt pe (63) {A separate relationship between specific volume and mass may be written by consi ering the total coniol volume, 1” 991 = const Bence av= = dt mae (63) Substituting equation (6.32) into equation (6.31) yields dud aut pav=o Since dt + p de = dq = 0, the process is reversible adiabatic. tn order to evaluate properties at any instant of time, the substance in the tank is assumed to be in equilbsium at that instant By using the reversible adiabatic properties for an ideal gas, Her @ aie Peau-w Sustiutng in equation (62) yes (gin) f- (A)F-F and integrating yields‘CHAPTER 6 / EUERGY AMALYSS OF OPEN AND CLOSED SYSTEMS Ina similar fashion Charging a Tank Let us consider the opposite situation, that of charging a tank. Figure 6.18 still applies, but the ow is into the costol volume. As before, we will neglect changes in ‘ineticand potential energies, note thatthe work iszero, andl the tank be adiabatic; rquation (6.27) becomes A this point, lt us assure that the properties in the line are constant with time (charging the tank does not affect chem). Tntograte from 0 10 (7 = Mags). With Ji, = cone, Thus , tty my (635) hh, = mats — mat (636 Let us apply this to the situation where the tank isinitaly evacuated (mm, = 0): thus, m= and gh = mats ‘Consider an idea! eas asthe substance entering the tamk (i nam, Hence, when charging tank, the final euilibiue temperature in the tank is ktimes theline temperature, Again equilibrium at any instant isassumed toexistin the tank, s0 properties are defined, . Tu 6D) tous, Example 6.9 [An adiabatic tank containing airs used to power an aie turbine during times of peak power demand, The tank has volume of 500 m? and contains ar at 1000 kPa and '500°K. Determine a) the mass remaining when the pressure reaches 100 kPa;(b) the emperature at ths instant; (c) the total work dane by the turbine, considering that it is also adiabatic and that all the ar exiting the tank also exits the turbine. Solution Given: tank containing sir at given conditions is discharge t0 a final presure ‘The tank isalso connected to an air turbine, and the Gacharged air Bowe through the surhine inds The mass and temperature of the air remaining in the tank at a certain pressure and the work done by the discharged air in the turbine. 6 Tans Row 991 ven Date: Figure 618 Assumptions: 1, Airis an ides! gos with constant specific heats 2. The heat lass from the control volume is 20, 4, allhe ir discharging rom the tank also discharges from th turbine, The turbine is viewed as initially having no air in it 4. The changes in kinetic and potential energies are zero, Analysis: Part (a): The mass remaining in the tank when the pressure reaches 100 kPa is determined from equation (6,34) with the value of = 1 for ai, found fom Tabe A _fonyt_( 100 "4 ma (2)"~Ga) oa m= 0.193 ms, “The inital mass io the tank may be evaluated using the ideals law 2 (4000 Pa)500) RT, (0.287 Ki/ke-KYS00°K) oeeore 1g = (0.193) 3484.3 kg) = 672.5 kg Part (b): The temperature may be calculate in several ways using the ideal-gas ‘eauation of state or equation (6.33). pay (100 kPay(S00 my nig (62S keNO287 ike r. 289°K nan (2) "= Go0-K) (EY sore GRar 6 TRANSIENT LOW 193 Part (c): Let's solve forthe turhine work numerically, using a spreadsheet. The turbine work will be calculated using equation (6.23) for polytepic open-system work. Foreach increment of tank presure, the mass of air removed ftom the tank is ‘determined, and the work done by the mass is calewated. The average tank pressure for each increment willbe used to calculate the turbine work. The sum ofthe Work for llth increments represents the total turbine work for the expansion fom 1000 kPa to 100 KPa, The data and equations are entered into the spreadsheet asshown on the previous pave “The resus are as flows: Comments: 1. Theieal-gas equation of state may be used st any instant as longs the properties are equilibrium ones. 2, Should the wrbine and tank motte adiabatic, ther means ta the fst aw mus bbe used to determine the heat low.‘CHAPTER 6 / ENERGY ANALYSS OF OFEN AND CLOSED SYSTEMS 3. The turbine is viewed 2s being within the contol volume with the tank and ‘contains no intial or final mass, whic allows the analysis to be direc, at CONCEPT QUESTIONS. 1. What isa polopic process? 2. What isthe difeence benseen 2 polyeopic proces for an ideal gas and a revenile aelabatic ae? 3. How: can an adahatic heat exchanger tense hea? 4. Airis compresed adiabatically. Wil te temperaare rie? Why! 5, Will a pressure drop across the tobe side ofa shelland-ube heat exchanger aft the siount of heat anstersd? 6. A tan nilly evacuate, is charged wih air a 300°K. When the tak i arsed, the temperature of the arin the tanks measured and found tobe 400°K. Wy? 7 Imunsteady Bow must the energy entesing the contol volume lta leaving? Does the sas How entering equal the mass lw leaving? 8, An adiabatic storage rank containing i at a igh pressure develops sigh lea, allowing Some ai to escape othe suroundings, Wil the tempersture in the tank change? Why? 9. Ina thostlng proces the enthalpies nto and out of te gontol volume are equal, but a trpertur change an osu Ean how te nee caso str ht awe PROBLEMS (51) 61 An inslated box containing carbo dioxide gas fills fiom a balloon 3.5 kr above the cai’ surface, Determine the emperatre rie ofthe carbon diode when the box hts the ground {62 _Airfrom ie gicharge of compressor enter Lm storage tank. Tail aipressue jn the tank i 500 kPa, andthe temperature is 6O0"K. The tank col, andthe internal energy desresses by 213 kg. Determine (a) Ue work done; (6) the Ret loss) the ‘hange of enthalpy; () the inal temperature 6.3 A igi, pefetly insulted system contias0.83 oy of liam st 1000 KPa The system receives 1000 J of paddle work. Determine the inal presse, (64 A constantpresure,adataic stom eootans 0.15 kg of ai a 150 APa. The system receives 20.79 kof paddle work The tempetuse ofthe ats intally278°K anally 416°K. Find the mechanical work anc the changes of internal energy and ental. 65 A cloed rig container bas a volume of | a and holds ae at 3448 kPa and 279°K, Heat isadded until the tempecature i 400°, Determine the heat added and te final 66 Apinonoyinder emu ui eeeatat acorn epee of500"Kandan jutial preaute of 200 KPa The foal volume O01 sy, and the tal volume (G07 ms Determine the hee ad work PROMS 8) 195 (6 Steam enters am adisbati tarbine at | MPa and 600°C and ents a 60 KP and 150°C Detar the work perk of seam. 68 Asam uebine receives ka/sof steam st2.0 MPa ad 60°Cand charges thesteam seesuturatedvaporat 100 kPa, Theat ns throuph te arbine KW. Determine the power 69 norte receives 3 hg/sofsteam at 06 MPa and 380°Canddcharesitat 100 KPa 200°C. Thee velocity ismeglsble an the het losis 250 ke. Determine the ex ‘eos 6.10 Airis compresed polytropically from 101 KPu and 23°C and delivered to tank at 1800 KPa and 75°C, Determine per go air (a) th eat removed during corapresion (the reversible work 6.11 A tank ith avolume of 50 mis being fled with iran ideal gs. Ata panicularinsant, theirin te tanhass temperature of "Kan 1380 kPa Atshisinstant he eesute isinerasng atarateof 138 KPa/s and the temperature isinrcsing ata ate 25 Ks Clout the ai lw into use tank at this stan in as 6.12 Airatapressureof 100 kPahasa volume of0.52 Their iscompresed in reversible fiahate mane until the temperatures 190°C. The reversible work 63 4, Deter Tie (a thoi emperature (8) teal mas: (che change of ater ens {613 icin a pston-yinder occupies 0.12 m7 at $52 kPa, The ar expands in a reversible ‘diate proces, doing work on the piston ual the valumeis 0.24 m?, Determine (2) ‘he work ofthe system: (D) the net work ifthe atmespheric presuce is 101 KPa (6.14 Thre mol of oxygen x cmpreseed in a pitan-ytnder ina eve adiabatic process from temperature of 300°K and a pressure of 102 KPu unt he final volume i oe. tenth the nial volume, Determine a) te Gal vempeazre;(b) the nal presse: (6) the ssn work {64 A seuba ankcomiias 5 kgofaie.Theairin the tankisiniialy at 15°C. Thetank set bear an engine exhaust line, and the tank's pressure coubles. Determine (2) the final temperature; (by) the change in internal eng () th heat ade. {616 Ina reversible adiabatic manner, 17.6 nP}min of sir ace compressed fom 277°K and 101 kPa to 700 kPa, Determine (ate fal teraperatre() the change of enthalpy: 6) the mass ow rat: (@) the power required. {617 Anakiabatc device look like an invert T with 3.03 kgs stom at 4 MPaand 600°C string from the top, ahd two steams exiting horizontally, one at 0.5 kal, 0.2 MPs fod 6°C. and the other at 0.2 MPa an an unknown temperature. Determine the un known temperature {648 A contol volume resives three sireams of steam (2,3). Poser preuced oF com umd, Eighe-undred kW of het leaves the conta volume, and two steam (1, $) leave. Determine the power, given that = 0.5 kus w= 400 mis p= 18 MPa, dry saturated vapor, m= 3.0BI, vz 0 ms 9, LO MPa, = 0.100 mfg my BD kgls, vj=Omis,p,= 600 KPA, Ty = 490°C; rig 40g, Y= 500 mi, 72 = 210 MPa, 7, = 300°C, = 4.8 kay, v= O mys ps = B00 KPa, T, ~ 500°C. 639 Anadabaic condenser receives 100 ys of steam 29% quality 4nd 60 MPa, Test teases at 0 kPt and 60°C. Te coling water enters at atmospenc pressure tnd 40°C and dscharpes at 60°C. Determine (a the heat raster (0) the Cog water ow196 COMPTER 6 / ENERGY ANALYSIS OF OPEN AND CLOSED SysTEMS {620 An aditatie rigid container, holding water initlly at 100 KPa and 20°C, reeves 200 kik of pale work: Datermina the fal tempera {621A pneumatic lit sytem is bing demonststed at sale show. The total oad is 70, and theif piston g 152 emia dlameter nd basa 202 diagram and determine the network and Reet Bows forthe cele kg of water vapor initlly a 1000 kPa i cooled at constant volume, V5 = P= (028 m. The temperature at sates IS0°C. The seem expands at constant presse from state 2 to sate 3 until the volume is 0.7519" Determine the specie 6si 656 657 6s 659 660 661 662 663 66 665 66 PROBLEMS (3) 199 ‘volumes and internal energies at cach state and the heat and work or each press. A piston-cliner containing 1.8 kg of water vapor operates ona three process cycle At ‘ate | the water i a sturaed sipor at IO MPA, which expands adiabatically 19 3 presure of 1000 KPa and a quality of 0.7817. At sis pint a constant prestue proces ‘cours until the specie volume a state 3 equals hat at stat L, Finally from sat 310 state I constant-volume heating oecur, Sketch he cyte on a Tv dag. Detenaine ‘the work and eat Fr each proces as Wall as he et Work fr the eee A fourprocesscyle using? kg of water operates with he alan procese: fom tate 1 state 2 constantvolume eating from SH KPa and 200°C ta 1000 kPa: from sate? to 3 coustntpressue cooling uot the wate isa saturated vapor from sate 310 4 ‘onstant-olume costing om tate 410 sthermalexpansion where Q, = 4478 Kd Sketch the eyele ona T-pdagam, Determine the spect volume un inna enery at ‘ach tate andthe net ork and total et ade forthe evs Anadibatic team turbine receives 10 g/s of team at SUOD kPa and 50°C. Thesteams ‘expands through te turbine tou prestuceof 1000 KPaandatemsperaure of 300°C where 2 ky/sisremoved, The remainder expands to S kPaanda quality of 0%. Determine the power produced by the turbine ‘Anaircomprestor receives? Yn of iat 100 KPa and 300°K and compresses itoa pressure of 100 kPa ia a reversible adiabatic poces. Heat rans ccers sd the iS temperate seduce by 40°K befor it eves the sompaesor, Deering the power Fequred to compress the ir and the total heat anserin the atercooer. What ielat- fing water ow rate i oguted inthe afereooe if the temperature se eos 28° to are An adiattic compressor receives |S Js of ale at 30°C and 101 KPa. The discharge ‘pressure is SS KPa, aa the power apie is 325 KW. What isthe discharge temper {A tefilgeration compressor reeives R (2 at 200 kPa and 0°C and discharges it at 1200 kPa and 50°C. The refrigerant flow rate at inlet condous is 001m The heat teanser rom the compressor tothe surroundings is? kik of retigerant, Determine (a) the pomer require (5) the vottme Now rate teat conditions. [A sompressorrecsves carbon dioxide gas at 140 KPa with a specie volume of 0.37 ‘2g ang compesis io a temperature of 28°K. The work per unit mat for om pression is 80 K/ke. The as enters through a 15-cm-hameter line wih a velo of O mysand leaves with 2 velocity of 28 mvs. Detar the beat raster io KW. ‘A hydeless ower plant has he hydraulic urbine located 60 m below he eevation| ofthe intake pipe. The emiameter pipe delivers water witha veloiy of 3 ays Temperature of 15°C o the turbine ‘The heat transfer between the tine tnd the ‘surroundings i eligible. Determine the power develope in KW A pump delivers 80 tess of water. The intake tothe pump 678 m bei the na ischarge. The inet and discharge pressure isessemialystrmspherc. and the tempera ‘ure of he water temains constant at 20°C during the proces, Determine the power required bythe pump. ‘An ciltranier pump uses | kW of power in transfering 5ky/s of ol through 22x Sdiametor pie. The changes in kinetic and potential enteric are exe nialy ser, snd the process edabatc- Additional, there sn appreciate temperature change inthe fl, whic sa density of 1500 kg/m Dewermine te change in resi rom inlet 0CCPTER 6 / ENERGY ANALYSI OF OPEN AND CLOSED SYSTEMS (667 An adiabatic heat exchanger receives 15 kg/min of R12 a 1000 KPa and 60°C and ‘condenses toa strated liquid at consant pressure This is accommpliahed by using st available at 30°C with low rate of? kas Determine the air est emperatuce fot the fest exchanges, 6.68 iris heated it flows sealy through a constat-aea duct of 175 em’ It enters at 200 4Pa,300°K. anda velocity 90 sand leavesat 150 KP and 360 m/s Determine the heat rans requir in kW (6.69 Anadiabsrccountriow heat exchanger recivs0.3s/6ofR 1292000 kPa and 90°C and discharges ita. sraratedlguld at 2000 KPa, Water enters at 25°C and leaves a 40°C, Determine (a) he water ow rate kgs (b) the het transfer from terete to the water in kW The coting unt ofan air conditioning system isa heat exchanges tht passes cover XIn FFD) In (VyV_) = OB113— ¥,= 0002 193m? RTs (0108 kpX0.287 ks /hg-KX940°K)/(0.002 193 m?) Pr 6150KPa T= 940°K State 3: Using the relationships fore reversible adiabatic process from state 210 state 3, the values of pressure and volume a sate 3 may be determined #-(8)""= Gas) 0.038 11 ee aay Gs) State 4: The heat out may be calculated from the thermal eficieney. Knowing this and the process, constanttemperature heat rejection, the value at state 4 may be {etermined. However, itis also posible to use the process relationships fom state to state 4 ia a manner analogous to going trom state 2 to state 3, ()-(G@)""- Gia) Similarly for pressure ¥,=0.027 91 kl 7 Penna y= PRT = (05 4gh0.287 AS /hg-K300°K)0.027 91m) pon 15824 Comment: One need not proceed in one direction around thecycle 10 find the eyele sate points. e Example 7.4 ‘A beat engine operating on the Camot cycle uses solar enemy as the source of high-temperature heat input. Thesolar irradiation. averaged over the day. hasa.value of .51 kW/m This providesenergy totheeycle ata uniform temperature of 450°K, “and the eyclereects eat to the environment at a temperature of 300°K. The engine produces 2000 KW of power. Determine the minimum area needed to provide this power222 CHAPTER 7 THE SECOND LAW OF THERMODYNAMICS AND THE CARNOT CYCLE Solution Given: & Carnot engine receiving heat from solar energy, operating between fixed temperature limits, nd producing power, Find: The land area required forthe collector to supply the heat for the power require. ‘Sketch and Given Data: mt ostmin? Fowre 78 Assumption: No energy i lost from the collector. Analysis: The beat ux in at any moment is found from the thermal efficiency of the eyele and the net paver required from the cycle. Thus, ‘Thisheat ux comes (rom the Solar radiation incident on the collector. An enctgy balance on the collector yielés 6000 kW = (0.51 KW/m?K4 m4) A= 1165 m? or about 2.9 acres Comment 1, Collectors with inge areas are required to generate power using solar ener: 2. The given average value of incident solat vadiatist way fo when the st was shining. During periods of darkness no pawer can be generated. = 115 REVERSED CARKOT ENGINE 223 7.6 REVERSED CARNOT ENGINE ‘The Carnot engine is a power-producing engine that uses heat supplied as an energy source and delivers mechanical work as an enerey output. When the Carnar eycle is reversed, mechanical work is supplied as an energy input and heat may be moved from one energy value (temperaturo) o another enersy value, Why da this? Consider the manner in which refrigerators operate. Enerav is supplied by an electric motor, “rivinga compressor, anc! the refrigerant (the working substance) picks up heat from {inside te efigerator ata low temperstureand discharges tata high temperature to ‘the condensing coilson the outside ofthe refigerator. We wll discuss actual refriger- ation systems later, but for now let us limie the discussion to the reversed Carnot exde, ‘The reversed Carnot cyele has all the same processes asthe power-producing Camat eyele, but the cycle aperates in the counterclockwise ditection. The p-1 iagram forthe eversed Camot engine is given in Figure 7.10. The purpose of the reversed Carnot engineis to remiove a quantity ofheatatalow temperature Q by supplying work. This result in rejection of heat at a high temperature Qu. The performance of reversed engines is denoted by the coefficient ‘of performance (COP), rather than an ficiency term. This has, however, the same purpose as ficiency — the desired effect divided by the cost of achieving te desired effect, For 8 reversed Carnot engine using an ideal gis, the working substance, the coefivient of performance is mRTeIn V2) PRTG Ta FI) = MRT pln yh) one Figure 7.10 A p-1’dinram forthe eversed Carot eyene ‘CHAPTER 7 / THE SECOND LAW OF THERMODYNAMICS AND THE CARWOT CYCLE “where the net work has been written asa postive quantity. Thus, the cosfcient of a performance ofa reversed Cart engine depends only on the absolute temperatures Of the heat reservoirs, The coellicient of performance of most reversed eycles is reat than unity “The reversed Carnot enginecan alsobe used 1 provide heat to warm space. The sctual device is called a fivas pump, where the low-temperature heat source is the surroundings, work sadded, and the heat oucof the cyle is discharged to thespace at ‘higher temperature and used for heating. Thus, the desired effet is heat out, The coefficient of performance ofa heat pump is one) were the net work i written asa positive quantity Example 7.5 Ahome requites 5.0 KW t0 maintain an indoor temperature of 21°C when the Dutside temperature is °C, A heat pump is used to provide the enespy. Determine the minimum power required. Solution Given: A heat pump providing energy for home heating with temperature limits and heat required noted, Find: The minimum power required to operate the heat pump. Sketch and Given Dates Assumption: The surroundings and the house are the low- and high-temperature heat reservoirs, respectively Anolysts: ‘The reversed Carnoteycte requires ie less power to moveheat from one Temperature to another. The house requizes 5.0 kW of heat out of the cycle to ‘maintain ielfat 21°C Its heat law differs from 5.0 KW, the house'stemperature 12 RST COROLLARY OF THE SECOND Law 225 will increase or decease. The reversed cycle is the system being analyzed thus, the heat out of the cyee isthe desired eect even though this becomes the heat into the house. The (COP), for the reversed Carnot eye is Goa We kw oi srs 387 KW Comments: |. Absolute temperatures must be used in the ealculations 2. The power requited in an actual heat pump wil be greater due to ieveriiltes. 7.7 FIRST COROLLARY OF THE SECOND LAW “The second law gives a sense of direction toa process whereas the fist lw does not. It also tellus that itis impossible to have a perpetual-motion machine of the second kind, one that violates the second la, The fist of two corollaries to this aw states It's impossible to construct an engine to operate between two et reservoirs, each having Gxed and wniorr temperature, that wll exceed he efiiency of a reversible ‘ cngine operating beweea the sme esos Figure 7.12ilustrates sucha situation. Note that the reversible engineisa Carnot engine, whereas the other engine may hase ireversibltes associated with i ow temaeate sta Figure 7.2 10 not engines, one eves : Inleand oneimeveribe opevaing betveca the sie temperature ists26 SECOND LAW OF THERMODYNAMICS AND THE CARNOT C¥CLE Assume thatthe ireversible engine has an eflciency greater than that ofthe reversible engine. Let 1 be the Work produced by the ineversible engine, while receiving heat Qy_and let I, be the work produced bythe reversible engine (Carnot) when receiving the same amount ofheat Qy. The assumption tells usthat W > Wy [Now run the reversible engine as «reversed Carnot engine so it wil supply the amount of heat, 10 the high-temperature reservoir, I would be possible o run the reversible engine by sapoying work from theireversible engine and stil have some net work remaining. This isa perpetwal-motion machine of the second kind and ‘cannot exist ecause it violates the second law of thermodynamics. Thus, the a sumption that If; > Tis not valid, and the frst corollary must be vai. 8 SECOND COROLLARY OF THE SECOND LAW ‘The second corollary ofthe second law states All eversle engines have the stm efcency when working between the same t99 constan-emperatre heat reer. “The proof ofthe proposition follows that ofthe frst corollary, Assume thatthe proposition is not true ina particular case, and then show that a perpetual-motion ‘machine of the second kind isa consequence. In tis case the irreversible engine is replaced by a Carnot engine of higher efficiency than the other reversible engine 7.9 THERMODYNAMIC TEMPERATURE SCALE ‘When discussing the zeroth of hermodynamiss, we aicovered that empertuce could be messed observing change inthe magnitude of prope. sal this isthe volume cbenge of mercaty oranotherliqid na thermometer. Temperature sles have een developed using varius properties of eierent substances. The Seles may bstandsrdizadat he boiling and ice pons of war, ut they wil ier at cihestemperatuelevelstispossbletodevelopa temperature ale thaisindepen tnt of stance propenins bt that relies om oversees ‘Weare atthe point where we can diseussathermodyami temperature saleby considering reversible engines operating between consi temperatre eat ree Noirs, Figue 7-1 ilustrates thi Thre reversible engine that produce wor, He Wy and Ty, are placed between constany temperature reser temperate T.2F;, Ts teopectvely. Engine 12 ecivesheat Qt temperature 7; and ees eat Of at temperature 7 while producing work Wa. Engine 23 receives heat Qp at temperate, and rejects heat Qa emperatare T, wile prone work Ty Enpine 13 rescbes est Q, at emperatre Ta eet heat Q, at emperate 7 while prodacne work I. Heat yi the same for engine 23 an engine 1, 8 eons by the fist Cray “he thermal een a reverie engine operating henson tan constant temperate reservoirs is been shown tobe futon of ony the temperatures of the reservoirs The thermal eficiency for engine 12, yi then ma ST,. TD) ony 1719 THERMODYNAMIC TEMPERATURE SCALE 227 & | 2 \e wp = Bi es i gure 7.13 Reversible engines operating between two temperature and the thermal eficiency i also Q Q 33) a, ‘ ‘and hence 2 ew functional relationship ¢ is shown o exist between the heat ratio tnd the temperatures ofthe heat reservoir by comparing equations(7.12)and (13). 2 @ {nthe same manner, relationships forthe other heat ratios and temperatures may be developed or deduced as TT) A relationship betwoen the three heat ratios is 2 _ uO, GOO ‘and substitution ofthe temperature equivalents yiekls WT) OT) ‘Tempereture T; mst cancel from the right-hand side ifthe equation isto maintain WT)228 CHAPTER 7 THE SECOND LAW OF THERMODYNANACS AND THE CARNOT CYCLE functional identity. Ths yekds a new relationship ar, 1) = (2 where w denotes the functional relationship “There are many Functional relationships that will satisfy equation (7.14). The simplest, andthe one used throughous this text, was proposed by Kelvin uD, 13) “Ths, 68 ‘and equation (7.12) becomes mrtg, “Thisisthe Kelvin temperature sale with which the vader fair, The limits are from 010 +, “Kelvin proposed another functional relationship that would permit the lower temperature limit tobe = ater tan geo. To Go this beintodued a ogame ‘eal with terperatore 6, The elatonshipberwen the scales may be shown as inne on Qe he (38) Equating equations (7.16) and (7.18) yields 40 an 8 —0=10(T))—In(T) and therefore ommn(ry+c ‘where Cis constant that determines the level of temperature corresponding to zero fon the logit temperate ae “The Kelvin temperatuce scale showod that it was possible to have an absolute= zero temperature that is independent of the properties of any substance. We must PROBLEMS (3) 229, sort, in the final analysis, to “thermometer” type instrument to measure temper- ‘ture sits impossible to design a heat engine running on the Carot cycle CONCEPT QUESTIONS CONCEPT QUESTIONS 0 1. Is ising te fist iw of thermodynamics scent 1 know whether a process can 22. & home refigertor may be viewed as rnwving work fom the surroundings and reeting heat othe srtoundings. Does ti iat the Segond law of thermody namics? ‘What makes some enrsy more valuable than other enersy? ‘What is 2 dhermal (heat) energy reservoir? Cana eat ensine operate with only a high-temperature heat reser? Explain the concept of term ficiency oa heat ensine [Aninventor creates hea engine wih thermal ficiency of 100%, Does his vot he fit nw orthermodynamics! The secon law of thermodynamics? Wey? 1. Would the thermal efcieney of «heat engine eeach 100% if al iveersblites were climinated? 9, Electric heaters are advertised as having an ficiency of L004. Is this posibe? Explain 10, 1s there a conceptual diference between efciency and coefcient of performance? Ex- pla 11, Why ae there me coefficient of performance for reversed heat engines? 12 Why doesan atl proces require more work thana corespondiog equlibvium procs? 18, Dessibe the diferencsbetwssa ntrmally, external, and italy reversible processes 14. & hot cup of esl on table coos to room temperature Is the process reversible? Why? 15, Acamofolsodsteon fable ina warm oom reaches room emperture. se process reversible? Why? 16, Ahouseis heated by abest pump, The owner tues down he house's eros Wihis Moc the performance oF the hear pump? Explain, 17, A refigeator is sooled by a reversed Carnot engine The thenmostat i ase in the refhgerated space, ows thse the performance of the reversed Carnot cycle? Explain 18, Solar every isto be the energy soute fora power pant. Two plansare beng conser, none system the solr collectors gather energy at 100°C andi the wie st 300°C. The (oxalenery collected ithe same in Both cars. Ione likely to have a higher effency? Explain PROBLEMS (SI: 7A ACarmotengine operates with0.138kgosieas the woranasubstance. tne pressure Solume atthe beginning of othermal expansion ae 2.1 MPa and 96 liters. The sr Tetaves as an ideal a8 the sink temperature is SO°C, and the heat added is 32 5(CHAPTER 7 / THE SECOND UAW OF THERMODYNAMICS AND THE CARNOT CYCLE Determine (athe source temperature) the cyl etcency 6) the preset the end of isothermal expansion; the ett rejected tothe sink pee ele 72 A Carnot engine produces 25 kW while operating between tempertuce fins of 1000" K and 300°K: Determine) te ea supplied per second (the het rejection 7.4 ACamot engine uss nitrogen a the working id. The hest suppl i $3 kl. and the adiabatic expansion ctis 16:1. The recivor perature 298°K. Deters (a) the "hema ficiency (6) Ue heat rested (6) the ork, 74 ACarmotengineusesairasthe workisg substance, reeives heat ata temperature of 315° , and ejects iat 65°C. The maximum posible escle presure i 60 MPa, and the rinimum volume is 0.95 ler Wien hoa s added the volume increases by 250%, Deiermin tho presuee and volume a each sate inthe ey, 7S A Carnot engine operses between temperatures of 1000°K snd 300°K, The engine ‘operates at 2000 rpm and develops 200 EW. The wal engine displacements such that ‘he mean elective pressures CU KPa, Determine (a) the cycle eens (8) the heat supplied (KW); (the total engine dnlacement on) 716 A Camotejele uses nirogen a the working substance. Te est spi 541. The teruperatre ofthe heat rejected i 21°C. an 1/0, 10. Determine a) the eye ei ‘eney (B) he temperature of eat aed the work, 172 lium is used in a Carnot engine where the volumes beginning with the constant. tempeatuse het addition are Fy ~ 03858 a, F3= 0130, Y;= 8.01, and Y= 557 me, Determine the thermal efceny 78 Airisusdina Carnot engine where 22 kl of hat recived at S60°K. Hest ejected 270°K. The dslacemest volume is 0.127 m. Determine () the work, (0) the mean fective pressure 719 Carnot engine operates berwcen temperature limits of 1200°K and 400°K, sing (08 ig of ar and runing at $00 pm. The pressure atthe beginning of eat dion 1500 kPaand atthe end of heat ation i 780 KPa, Determine (a) te Best aed pet Ons + Ons 62 Equations (8.1) and (8.2) may be combined as O5= Qn + On > Analyzing Cammot engine A, we find Out A= From the Carnot engine efficiency hense oo-0s (8-08) “4 and similarly, for Carnot engine B, 2), (2 05=0n (2) = en(2) 5 Consider te lgebriesummaion frie es Soving into an out ofthe Sak Lev thea Grete te sk bones rt age sem) at the fas rand Dubosc (sth ae month enrthe sae). The some Torr se hel wie Ons + Ons + Oss =0 @6 ‘Substituting equation (8.4) and equation (8.5) in equation (8.6) yields Oa 5 Ose +S en ‘quation (8) was developed for three neat reservors and could be expanded fr heat reservoirs, This means that there would be n — 1 temperatures at which heat could be aed to the stem 2 pEs0 [As the nuinber of heat reservoirs becomes larg, the heat transferred at any given reservoir becomies stall. Taking the limit as» becomes infinitely larg, Q becomes infinitesimally small, and @ 8Q Se ra aaa 7 ea) 50. 2 29 Equation (8.8) isthe Claustus imequatty 2 DERIVATION OF ENTROPY ‘The definition of entropy was developed by applying the Clauss inequality toa cyclic process, Figure 8. illustrates a tWo-proces cycle, composed ofreveribe paths A and B. Since the cycle is reversible, it s posible to proceed in the clockwise or counterclockwise direction. Point Pislocated on path 4. the system proceeds an infinitesimal distance from ‘Pin the clockwise direction, an amount of heat 60, will be added. [7 the direction is reversed —and the system returns that infinitesimal distance to point P—an infini= ‘esimal amount of heat 3Q,is removed, Figure 6.2 Two pats, and B joining sales | and 2.240 Ccuarren & /euory Heat added is positive, and eat removed is negative; so 01 ~ 60. Applying the Clausius inequality co the cycle, Ss t., . $igeco in 10, on ‘There is only one solution that satisfies both equations (8.9) and (8.10) 404 7 Since it woud be possible cain the sme re forthe sountclockvs ie fon the exresion maybe vey in genera 5g fio ws ee LOL £6) 28 Since the paths 4 and B are arbitrary pats, for any path between the points {and 2 780. f* °2) 5 “(8) nT OWATH NATH Ting ms test wson cpa ae ane deed ana *2) eo “fl © s 3 CALCULATION OF ENTROPY CHANGE FOR IDEAL GASES 241 Although the quantity (5Q/T)qy may denote a diferentia change inthe prop- ‘ty She property difference is described by equation (8.13) This poses na problem in undergraduate thermodynamis, since the analysis of problems uses the entropy siference. However, the resolution ofthis dilemma remains « point of interest, Let us now apply the Clausius inequality to a system operating on a cycle ‘composed of a reversible path and an ireversible path B, #8) [a However, foran irreversible path 4Q/Teannot be evaluated. Te entropy change for an irreversible process between sates Land 2 is 5-599), ‘The equality sian may be included if we wrie the previous equation far both vers ible an ireversibie stutions ss ['(2) a ase (2). enn) ‘Wemay reach several conclusions regarding the entropy change ofasystem, For adiabatic closed systems, the entropy will increase due to internal ieteversibiites, Only for revesibie adiabatic processes will dS = 0. 8.3 CALCULATION OF ENTROPY CHANGE FOR IDEAL GASES ‘Thus far we have not calculated the value of entropy, or the difference in entropy between two states for a closed system. We will fist calculate the enteopy'of eases, using the idealgas laws and the gas tables, and then calculate the entropy of pure substances, The fist lw for a closed system is so=du+ew Fora reversible process, and considering only mechanical work, this becomes Pasa d+ pav orn Equation (8.15) is avery important thermodynamic relation. A. second importantar uses $ /eutsory relation is dH= aU + pdV+Vdo anc for reversible processes, with only mechanical work, this becomes Tas: WV dp : ers the idea-gas equation of state is used, p= mT, end the change of enthalpy ‘nc! internal energy is written for an ideal gas, equations (8.15) and (8.16) become, respectively w asm me 2 me E an and as a _ ape? me, mea er8) touring been sates | and 2 wit consant specie hats and mses 2) «main (22 SHS, rots (2) xn (2) e19) 5-5, min (2) ~ mein (#2) ez ‘Thus there are to equations describing the change ofentropy foran ideal sin ‘closed system. The particular equation to use isthe one that will make the soliton simplest “The eo tables sccount forthe variton of specific heat with tempertue. I austion (18) partially iterated a lows, ~ sem {eee maia (2 sim [6p min (2) an from the sabes, a fot-o-a, then ~S.=mids~4) men (2) ary y=) 2 ry For convenience, values ofthe temperaturelependent integral ar listed in the si 12.3 CALCULATION OF ENTROPY CHANGE FOR IDEAL GASES 243, fs tables under the heading d, where 7 dt 6 [8 Example 8.1 Calculate the change of entrapy of 3 kg ofa that changes state rom 300° K and. 100 Pa to 800°K and 300 kPa Solution Given: Ai changing tate with both states completely identified Find: “The change of entropy ofthe aie, ‘Sketch and Given Datas ie Tomar 7 Figure 82 Assumption: Air behaves as an idea gas ‘The change of entropy ofan ideal gas is given by equations (8.19). (8.20), 21), In equation (8.21) the variation of specific Reas with temperature is included, Solve for the air volume at each state using the ideal-gas equation of sate, 7, RT — (3 kg 0.287 Pee K 300K) (100 KN?) 2583 net wel oa = (3 Fg (0.287 LI fg 1(800°K (500 Kes?)2a Denali ni(2) + nti) omo-r76uaesn (22) +nieas wri (22) SS LST RIK From equation 8.20) som Ba ) s.=oxeuor arena (22) 027 wag (22) Ss S~ Se LST Using equation (8.21) requires use of Table 4.2 AAU 3OO°K, oh, = 2.5153 KI /kp-K: at 800°K, d= 3.5312 KI /keK, S,—S, = baXG.S312 ~ 2.5153 J eg-K) ~ kg 0.287 KI eK) Im (9) S,-S,= 166KI/K Using TK Solver and the model AIR-TK, the change in entropy eam be easily calculate. {04 RELATVE PRESSURE AND RELATIVE SPECIFIC VOLUME 245 hus “The change in entropy for the 3 kg 5,—S,=0G kaNO.58616 KI Comments 1. Te problems where thee isa sigoificant temperature variation, as there isi this ‘example, the variation of specific heat with temperature basa significant effect in culating the change of entropy. In this case the diference is nearly 6. When the initial and final states ofa system ae given, the entropy change may be computed whether o¢ tot the process the system underwent was reversible. Em tropy isa system property and as such daes aot depend on the path taken the system in changing state, snd a reversible path may be chosen. Ths is implicit in the derivation of the expression for change of entropy e 8.4 RELATIVE PRESSURE AND RELATIVE SPECIFIC VOLUME “The gas tables also give the means of caleulating an isenirpie process from state Lo state 2. Foran isentropic process, AS 0; hence The relative pressure, p, is defined as =mn(2)=2 nin) =tn(2)=€ where gp isa reference tate, Then w(is) wa t-(8) = ‘There is also a relative specific volume v, Hence, (02426 coarten 8 /exrROrY Example 8.2 ‘Three lbm/sec of airexpands isentropically through a nozzle from 1000°R, 200 psa, and negligible velocity 20psia. Determine the velocity exiting the nozzle, using the fs tables as appropriate. Solution Given "Ais lowing sentopically through a nozzle from given inlet conditions oan exit pressure. Fi tr The ar velocity exiting the nozzle Sketch and Given Data: i jatteae {\__ BST ap were he pe oe eo Fowesa Assumption |. Ai behaves as an idea! gas with variable specific heats. 2, The negligible infet velocity allows us to neglect inlet kinetic energy 3; Inlet aad ext potential energy changes are negligible, 4. There is no heat flow, as isentropic denotes reversible adiabatic conditions, 5. The Now is steady, and steady-state conditions apply 6, There is no work crossing the comteol volume, Analysis: The fst la Foran open system yields G+ rill + (hed, + ped) = H+ mls + keds + (pe) Invoking the stated assumptions yields (hed (hi = ha) ‘The substance i an ideal gas with variable specific heats. The enthalpy and relative pressure at state | may be read directly from the table, yielding By = 12298 2, = 240.98 autora sic is on sitesi (4 RELATIVE PRESSURE AND RELATIVE SPECINC VOLUME 247 ‘The process from state J to state 2 =p Pam Pa isentropic, thus 2.298(20/200) hy = 124.75 Beustbm ‘Substituting into the fistlaw equation yields 2b = 240.98 — 124.75 Btu $b = toss — 12125 Busi a= 2812 see Solve the problem using TK Solver and AIR.TK. ‘Therefore, since DELN is ~115.61 Buu/tbm, va 2405 scoEntropy Change for incompres: ‘ouarren 8 /emoey Comments: 1. The relative pressure and relative specitic volume ratios may be used only for isentropic processes, 2, The temperature leaving the nozzle isquite cool compared tothe inlet conditions. “The entropy increase caused by the decreasing pressure i balanced bythe entropy decrease associated with lower emperatute, = 8.5 ENTROPY OF A PURE SUBSTANCE Entropy has been defined as a property ofa system, and the specific entropy is tabulated in the tables of thermodynamic properties, Since entropy is @ property it may be calculated for any quality within the saturated region, It is listed in the compressed liquid and superheated vapor tables. Figure 8,5 illustrates a Ts diagram for steam, Another frequently used chart for slam is the hs diagram, called the Moller diggrar,illustcated in Figure $.6. Inspection shows a disadvantage ofthe ‘Moller diagram isthat it cannot bo used for steam witha quality of SO% or less Aswe willse inter chapters, the Moller diagram isthe traditional means availabe forthe solution of steam turbine problems. The 7s diagram usually oes not list specific volume, a disadvantage i its use. However, both charts are very useful for particular problems nd willbe used forthem. Thecharssare listed in Appendix Tables B.1 and B2. le Substances ‘The internal energy ofa substance isa function of temperature and specific volume, 1(T, 0). Ifthe specific volume iscanstant, the internal energy ia function of temper. Figure 85 A Ts diagram for water. SS uTROPY OF A PURE SUBSTANCE 249 Figure 84 An hs, of Moller, agram for water ture only = u(T),asis the specific heat, e= (7), The change ofisternal energy dum eT) aT From the ist law for lose systems, Tas= tut pao de=0 fore thos, , is= (PE asa) G Integrating this between states J and 2 yields _, - Ppanar Bae OT and f(T) a constant fan average value over the temperature range is ofen used), the change of entropy for an incompressile substance becomes aos relnh/T) (025) Example 8.3 Twelve ke/min of R12 flows through an evaporator coil at constant pressure. The {net conditions are 308 6kPaand 30% quality, and the refigerantexitsasa ssturated vapor. Determine the change of entropy aeross he evaporator and the het low rate ta the evaporator. Solution Given: Retrigerant flowing through an evaporator, roceiving heat, and evaporating from given intial state 10 a given fina state at constant pressure250° cnabreR 8 enraary Find: The change in entropy across he evaporator an the heat Now rate Sketch and Given Dates | 4 Saami, aon Assumptions 1, The conditions are steady-state 2, Reliigerant 12 isa pure substance, and the sates are equilibrium ones, sotablesoF| properties may be used, 5, The changes in potential and kinetie energies may be neslecte, 4. The work done at constant pressure in an open system is er. Analysis: The fest aw for an open system is O+ mh, Hed, + load] = WH mith + eed + (pe) Solving forthe heat flow subject to the assumptions above yields = rid, =) ‘The properties for R 12 found fom Table A.11 are 2h, = 36.022 53 Pkg + (0.3N151.376 Kd fk) = 0.1418 + (0.390.5582) = 03081 KI/Ae-K = 187.397 kg 0.9960 KI/kgeK 143 bd eg The heat flow is (12 hain 187.397 — 81.43 KI) oymiay @ = 2119 EW Te change of entropy is rey 9p 2H DAB EK orgy Because R 12 sa pure substance, the process is not only constant-pressure but 126 FURTHER DISCUSSION OF THE SECOND LAW FOR CLOSED SYSTINS 254 ‘constant-temperature. In this case the equation for heat in terms of entropy may be Jur fre Ts) ‘Tn the case where flow is occurring, Q= rig. Checking the results in this case, the ‘temperature of evaporation is 0°C ot 273.15°K, hence = WTI s, = 5) = QTLAS*KYO.776 KW /K} Comments: forT=C Lag kW 1. When a reversible process is constant-emperature the heat low may be found from the F dsequation Ithis process were not reversible, the equation would not be applicable In actual procesesa pressure deop oecurs: hence the process would be neither constant-pressnre nor constan-temiperatur. 2. Absolute temperatures must always be used in entropy calculations 8,6 FURTHER DISCUSSION OF THE SECOND LAW FOR CLOSED SYSTEMS a [QL ), si [' (2) +3500 aay Let us evaluate the ireversible heat term. Assume thatthe system receives heat at temperature 7, This temperature is the system temperature atthe boundary AS “This reduces to s282 resiving the hes. For one beat sore a «Rue emperaie, uation (8.27) boone ase 5 Bh 85 eam itis poste to exe ths by sonsiderng.a sytem that has several et Haws, each at irene bt conan npemture Baton 628) Besse 5-5 $24 AS e29 equation (8.29) isciretsted with eapec'o ime pig yas mnatime-ratebasis 2 Le‘ usapply equation (8.28) toa reservoirsupplving heat Q,a¢ perature 10 «system, In this situation we wish to determine the entropy change ofthe reservoir. ‘The entropy production with the reservoir is ero; thereare nointernalinreverii ties, for its ata fixed ancl constant temperature 2 wT As, (231) ‘Consider that the reservoir and the system are two subnystems within an isolated, ‘adiabatic, constant-mass sytem. Comparing equations (8.28) and (8.31) wee that the entropy-production term is due to internal system inteversbiites, Lets consider that an isolated system, one thats closed, is aciabatic and has no ‘energy low across its boundary. We know from equation (8.146) that B= 0 (eam) AS =O (e325) ‘The system may have several pars toi, that is / subsystems, s0 i we let equation (6.32) apply tothe overall system, then Suu = JASE 0~ AS yg (035 Example 8.4 A Sg, stel billet is heated 10 1200°K and then quenched by placing it in 50 kg of| Water, initially a¢ 20°C, Determine the entropy change a the water and of the billet and the entropy-production tem. The average specific heat of see is 0.5 /kg-K. Solution Given: A bested stel billet of known mass and temperature is plaed in cool water with a known initial temperature, 186 FURTHER DISCUSSION OF THE SECOND LaW FOR CLOSED SYSTEMS 253 Find: The change ofenteopy ofthe water and metal, 95 wellas the entropy produc- tiom due to ieversbilitis in heat transer. Sketch and Given Data: Assumptions: {The metal and water form two subsystems within an isolated system, 2. The changes in kinetic and potential energies are zero. 3. No work i done “4. No heat flux crosses the boundary formed by these two subsystems. Analysis: To determine the entropy change ofthe subsystem, the final emperature ‘must be found, The first law for a closed system is Q=AU+AKE +APE. +17 ‘The heat, work, and changes in kinetic andl potential energies are zero, making AU zer0, The total change of internal eneray isthe sum ofthe subsystem Ls. Thus, AU caer + AU ngs 0 1, wat 20°C = 82.9 1 ag 5% Spat 20°C = 0.2914 II ka K ‘Substitute these values into the equation (a=) + me (7, T)=0254 cuasTen a /enraoey Solve by trial and errr for Ts, T= 303.7°K 128.0 kg 18 30.7°C = 0.4424 Kt Jig K ‘The entropy changes may be calculated os Sea = (50 kaX0.4424 ~ 0.2914 Kd /kgeK) = 7.55 K/K AS = (5 KeNO.S Kd /RE-K I [303.7/1200] ~~ 3.44 KF /K There is no heat transfer crossing the Boundary, s0 the entropy production isthe um ofthe individual entropy-change terms of the subsysiems, yielding MSyep = 7.55 — 3.44 4.1 IK ‘The entropy change of the watercan also be calculated using TK Solver and the model SATSTM.TK as follows: Comment: 1. Te steel decreases in entropy because the temperature drops, but the water increase exceeds it by the amount ofthe entropy-production term. 6.7 equupnum state 255, 2. Forliquid waterat eatvelylow temperaturessuch asin thisexample, the internal energy may be represented a8 cy 7, Where ¢, ~ 4.186 kl /kg-K. Even at clevated temperatures an average specific heat may'be used, hut it wil have a diferent ‘numerical value than the one given, = 8.7 EQUILIBRIUM STATE CCausius stare his investigation of systems and developed, or discovered the peor «ey of entropy in order to determine Whether an isolated system vasin equilbriur, Since dS'=(3Q/T ys there are two methods by which dS will be nonzero. One ‘method can bean exchange of heat JQ between the system and the surroundings. The stem s isolated, however, and so therecan ben energy tansferbetween thesssiem land the surroundings. The other method requires a temperature differential within thesystem, This would cause an irreversible enerpy flow within the system and result {na change in the system temperature, Thus, tis omly by an imeversble process that the entropy ofthe system wil increase. “The follawing conclusions about the change in entcopy’and system equilibrium ray be made, 1, When theentropy ofan isolated syStem isa its maximum value, nochange in 2, When itis possible for theentropy ofan isolated system to inerase, thesystem cannot be ina state of equilibrium, and its posible for a change of system Figure &.9 illustrates an entropy equilibrium surface. The system is characterized by temperature T, and pressure py. Ifthe sytem isin equilibrium, itis denoted by poim. Aon the equilbriom surface. the system isnt in equilibrium, however, thas obe below the equilibrium surface, as illustrated by point B. A change may occur that ‘woul bring the system 10 the equilibrium surface; however, we cannot determine ‘whether or no it will occur, Note that the entropy is @ maximus for its state ifthe Figure 9 An eauibrumy surtice with fates A and C on the surface dnd ste D Iw the surface256 cHaPTER 8 /ewTROPY temperature or pressure were different, another maximum value ofentropy for that slate ould be the equilibrium Value, such as point C. The fllowing statements summarize entropy changes ofa closed system 1. Theeniropy wil decrease when heat is removed ftom the system, all process being reversible ones, 2, The enitopy will remain constant when reversible adiabatic processes occur vothin dhe system 3, The entropy will increase when heat is added to the system, reversibly or icreversiby 4, The entropy of an isolated system will increase when ireversble processes eeu within it ‘Statement | requires the restriction of reversibility because iereversibilties Within the system may cause an entropy inerease, and although the heat removal results in en ‘entropy decrease, the net entropy change could be postive or negative, dependingon the magnitude ofeact term, Let us examine in more detil what constitute ireversibilites.In Chapter 3 we ‘examined a quas-equilibriur process and found tis to be an example ofa reversible ‘proces, sith an irreversible proces being one where mechanical, thermal, or chemi- ‘al equilibrium does no existas the system changes tate. Thsis one typeof irevers- ‘bility. A second type is caused by the natural Gisipative effects ofa substance. For insane, frition dissipates some useful energy (work) into a less useful form (heat) ‘This characterizes all dissipative effects. Many common phenomena demonstrate this dissipative effect—springs are not truly elastic, inductors contain some resist- ance, viscous effects appear in foing Mus ‘Al actual processes comin some ofthese or similaeiveversiilces. Thus, fora process to be truly reversible, it must meet wo general criteria it must be quasi librium and it mast be nondissipative. This isnot possible; thus, reversible processes become a limit that we cannot reach and can only strive for. 8.8 CARNOT CYCLE USING T-5 COORDINATES ‘One ofthe great advantages of a TS uiagram is that reversible heat transfer may be represented Since Qua — /T dS, these are the natural coordinates for reversible heat flow. When talking about the Camot cycle, we had to invoke the ideal-gas law to determine the efciency, This is to longer necessary. Figure 8.10 illustrates the ‘Carnot eyele on the TS coordinates. Notice thatthe reversible adiabatic process, a ‘constant-entropy o¢ isentropic process, isa straight vertical line From the equation for revesibie heat transfer, oo= Tas 2 9 HEAT AND WORK AS AREAS — 257 Figure 6.10 A 7S diagram forthe Carmo cycle Hence i= TulS.- 8) ey and Qs" TelS. 55) 35) but and recalling hat 638) [Not surprisingly, the result is obtained more directly when using the proper therm0~ dynamic coordinate. In this ease the ieal-as law didnot have to be invoked, thus Semonsivating that equation (8.36) is valid reyardiess ofthe working fuid is the Carnot engine: 8.9 HEAT AND WORK AS AREAS “That the work sequal othe algebraic sum of the heat supplied and heat ejected my be demonsirated graphically The enclosed area in Figure 8 (a) represents the heat Supplied, The enclosed area in Figure 8.11(b) represents the heat rejected Siace heat jn's postive and heat out is negative the two areas, when added, yield the net work, shown in Figure 8.11()258 cuapTen a /enrnory Figure 6.11 A graphical illustration thet he network she sum ofthe heats 8.10 THE SECOND LAW FOR OPEN SYSTEMS We have considered the second law of thermodynamics fr closed systems let us exten this to open systems Figure 812 illseates a general ope ssn, contol ‘volume located ina thoving Hui with hea and work being done. “The second law may be stated for constant mass as Bor. $0 Be Ot OS 37 ‘Themassin the contol vlumeat times hats the contcot mass scoastant We ll develop anotherexpresionfortheentopy of te contol mass and om develop the expression ofthe second la fr open s}stems. Figure 6.12 A control volume late in a moving fui 840 THE SECORD LAW FoR OFEN SYSTEMS 259 “The entropy of the contol mass at time ¢is Soxue™ Saat Sie* Sa (38) ‘The term Sy, 8 20", soit may be included. At time 1+ As, Seaeosr™ Sasoas + Sicsas + Suess (039) ‘Again, Size is 8 convenient zero 10 have in the equation. Take the difference ‘between equations (8.38) and (8.39) and dive by Ay, aking the limit as At ap- ‘roaches 2e¢0, This yields en _ 4 Ou «0 a at a on “The negative sign on dS; tis due toa physical decrease inthe quantity (Sy, Si) Let us adopt the following convention: s=ms Sim aa ‘As Arapproaches er0, region IL coincides withthe contro volume, and regions ‘and IIT represent flow in and out of the cOtrol volume, respectively. Equation (8.37) becomes (0.02) Forno heat transfer across the contro surface, the surface ofthe control volume, equation (8.42) becomes Ils, ~ 5) BS aa3ay aes (6.430) ‘Thus for steady, one-dimensional, adiabatic low, the second law tells us thatthe ‘entropy inreases or remains constant; it cannot decreas. Exemple 8.5 Steam entersa 6-in-diameter pipe asa saturated vaporat20 psa witha velocity of 0 f/see. The steam exits the pipe at 14.7 psa witha quality of 95%, Heat loss rom the pipe, surlawe temperatuse 220°, occurs by convection to the surroundings ot 80°F. etermine () the entropy production across the pipes (b) the entropy change of the surroundings.260 ccuarren 8 ENTROPY Solution Giver: & pipe has steam enter and exit at known conditions. The pipe loses heat Find: Entropy production due to iereversibilites, considering the pipe as an open ‘system, and the entropy chenge ofthe surroundings due to heat transfer from the Pipe Sketch and Given Dara Figure a3 Assumptions: Equilibrium steam property values may’be used 2, The flow issteady,and changes in kinetic and potential energies may be neglected 53. There is no work flow crossing the system's boundary. 44 The heat flow from the system occurs at a constant and uniform temperature, Analysis: The change of entropy across the pipe may be calculated using equation (842 ene risa 5) = 2b AS “The heat fax can be determined from an open system, frstla analysis across the control volume for steady-state conditions, Or mh, + Ke}, + (ped) = W'+ rill + (keds + (pe);] Applying the assumptions reduces this to Om ris =f) “The mass low rate may be determined from the equation for conservation of mass, {230 THE SECOND LAW FOR OPEN SYSTEMS 261 since we know the velocity, specifi volume, and cross-sectional area, The steam properties entering and leaving the pipe are ‘n= hy at 20 pia ~ 11364 Bru/Tom 5, 4, 2020 psia 1.7318 Bru /tbm-R 6, 9 8120 psia = 20.094 /Ibm hy 2) = 11020 Bea bmn hy-+ she at 14.7 psia = 180.35 + 0.9500 s+ xg at 14.7 psia = 0.31192 +0.95(1.4445) ~ 1.6842 Bru/Tomm-R The cross-sectional area is Faye owen The mas oni pin 8 UAE BOD AL 3 en (20,096 83/ibm) and the heat fu is determined by @ = nil, — fy) = (0.293 Ibm /seeX1 102.0 — 1156.4 Bru/bm) = —15.94 Beu/see ‘and the change of entropy across the pipe is (5, ~ 5) = (0.293 fom see 1.6842 ~ 1.7318 Bru/Ibe-R) = —0.0139 Btu/seoR Applying equation (8.42) yields the solution forthe entropy production = sy- 8 P62— 3) = FEF AS 15.94 Buussec 00139 Buu ee R =~ ESTEE aS Sona = + 0.0095 Bru/sec-R “The surroundings area constants system; hens appving equation (6.31, wri fen witha heat ont Becomes =-% Sue T, ARISES 0.0005 Biujsec-R Sun = Comments: 1. The entropy change of the surroundings i always positive because of best flow into the surroundings. 2, Ifthe pipe were insulated —adiabatie—the enthalpy ofthe steam leaving the pipe262. HAPTER 8 / ENTROPY ‘would be the same as he inlet condition, but the steam would be superheated at the loner exit pressure. A glance at the stcam tables shows that the enttopy increases; thus entropy production always occurs, except for eversible adiabatic flow conditions = 8.11 THIRD LAW OF THERMODYNAMICS ‘The thir la of thermos amie allows the calculation of absolute entropy. The ‘Nernst postulate of the third law is a cabot entpy ofa pare cline sb compete epi i at zero degrees absolute. “ Although a complete discussion of the hid law adits implications is beyond the scope ofthiston team beseen ha the absolute entropy of substance at somestate 2 may be determined as follows: ae (re = However, -se [8 (an but = 0,20 heabolate alo, may be determin uation (48 and the able au a mas by dermal fom equation 8 Soscomnane he Abrus vale of may be foun inh some mane 8.12 FURTHER CONSIDERATIONS Hersofore wehaveconidee¢ stem bean amount ofied matsorspce mo likly an engine of a tltvely small ize, Consider now tha the seme te univer, wich bigot Od as, aes te dfion of taen Wit eae Ai the process mini any sym andthe univene were enone eee Sis, there would be no ince n envopy. Acbal puceuss ae eae howeter and to ther ira contin Ieee ie enoy Oke one as tian thatthe enon mst have been ena conta or Sold sa increasing nos, eons geculing abot icentenyotbccar eres minimize orginal aloughts yond he seope ois act tres rola from ich many inceing dus and spesadone may Mone Entropy and Disorder 11s posable to consider entropy fiom a probabilistic viewpoint, which leads to viewing it asa measure of disorder or chaos, Todo thisle's start with an insulated or adinbatic container with Ig mol of some gasinside it. Furthermore let us divide the 12 FuRtHta conSOERATIONS 263 container into two equal volumes and let he gas be equally divided between the two Volumes. The division between the two volumes will be a membrane with a smatl hole in it Furthermore, let us imagine that we paint a molecule, lorated in the Tefchand volume, white, Iwill bounce around the container, colliding withthe other molecules and the container walls, We assume there are no external forces, 0 all Tocations are equally possible, andthe molecule will occupy all these locations evens tually Itcan also go through the hole, an, since the volumesare equal we esmexpect toffind the molecule half ofthe time oa the right side and hal of the ime on the left side ofthe container. Tha, the probability that iis on the right side i 1:2 ‘Nov fetus imagine that another molecule is painted dierent color and that it too will migrate between both volumes and have a probability of being on the right-hand side oft: 2. The probability that both molecules wil be on the right-hand fide is} X 1 ~ 4 Iwe consider mare molecules, say three identifiable molecules, the probability of finding all three on the same sie is(2)* =f, Ife now extend this to 7 rolecules, the probability is (3). The probability of finding the entire grara mole of ‘molecules on one sie is extremely seal: (4°, Since there are no leaks, the probability of finding all the molecules in the ceomtainer is certain, ot 1:1. ee posible to show that fr two volumes defining the tnclosure, Vand F, the probability of nding all the molecules onthe right-hand side i (74/1), _ [Fetus now consider that we observe te expansion ofthe gas from volume V 10 inthis adiahaticcontainer. The gasisgoine Irom a state of low probability igh probability, 9, = | volume to asate of Ina ¥ s-an(') Let the ratio Rj be equal toa constant &, called the Boltzmann constant, Thus, the entropy ofa state may be related to its probability by Entropy increases for any spontaneous process, since it goes from a state of lower probability to one of higher probability:254 ‘coseres a /enory How does thats chaos? The nse is in understanding envopy sel: sonshp 0 probly. Le senamin soe, Have ou noted ta aces ones Ete ine dot make an fino keep hem aes? Conse neon th feshsundchaisin neat avs atthe sexing ais prod Nov loka ede the he pro ver ane the tors have Te sder has nce, ne Shas and desks reno lng net row, some ate ted i ages so puedo iow do we meanite his arde? Consider the followin situation. You nety platen meson outset al isnghens up Theyar en knock ese 'Whavsthe roby of nding tema eae upon he oe’ The answers) eratout one in a thousnd Ths the probably for sre suc tee ha that for one 'rcompariog order and entropy, we se tht when a stem changes espe tances roma ato ower peo of een toast aes brat. Alo, the of highs prota fs move dere Ths We nd thas the eno oa stem nce, oe disorder chaos CONCEPT QUESTIONS 1. Explain sate unstable, and masa 2. How is the Clauss inequality eared to entropy? 3. sentry a propery? Why? 4. What i am isolated stem? 5. Papin entropy 02 kypersen, 6, Isthere x conservation ot entopy pincipe fr oat systems? 7, What efit dees work have an etn production? 8. What are the causes of entropy prosuction? 9. 1st tue that the ehange of entropy fora closed system is identical for al processes ‘operating beeen the same nil nd alte? 1, Is ictus that the entropy change of close system cannot be negative? 11, Iscpossinte to conceive ofa proessthat would violate the second law of thermodynamics Due mot the rs 0? Expl, ° ilibium, 12 Itssetha change ofeneopy asta expense fom hearst he suroundings sequal and opposite to te entropy change sucroundings esi ue, this het tne” Sees 13. Writethesecond aw focosed systems in terms of entropy change foraabaie process 14. Write the second aw fr seadstat adiabatic, open systems in tems of entropy 18, Is the expreson Tat = dirt p de restrited to ceain types of proves? Explain. 16, & proves internally reversible and adiabatic. Is this the same as tentrope? Explain 17, Twosotktbivks at tne sume materi an identical mass but aiferenttemperacresare broueht together a aisbatie container until they reach thermal equlibram mth one another Doss the entropy decreas of one Block equal the entopy increase othe tke? lai pda PROBLEWS (3) 265 18, Using te relationship between speci heats show that equations (19) and (6.20) are idence 18, What does the property mem in the gs ables oe ae? 20, What ae the Himitacons ow using p, ans inthe gas tables fr ait? 21, Consider an del gaswith constant esc heats undereoing an soermal proces. Dost the entropy change? OBLEMS (SI 8.1 Two kyofa gsis conte fom 500°C 1 200°C atconstantpresursin a heat exchanger Desermine the change of entropy f(a as (b) arb diode) hea 2 Calulte the change in entropy por kg beeen 250°K apa 75 KPa and 750°K and 300 Pa using the ideal gas aw and the gas tables frat. 18.3 entropic compresion ofa ours Deere the emperrure ati that allows this Sftbe resus rat is stand the gas sta ai (b) propane: c) helium 84 An isotirmal expansion of ar occurs is 2 ision-slindee om 298°K and S00 AP 0 225 kPa. Determine the change of etcops ner KE 185A pison-ylnder arrangement bas been develope to compres air adiabatically from S0PC and L00 kPa to 430 kPa with 120k ot work. this posse” 86 Anisothermal compression process of $0 ka of nieogen fiom 305°K and 1208Pa 0 {SU kPa ossursin age water cooled compressor Determine (a) the charge of enzopy (6) the power egies 7A pistor-5 change oF ach 5 Airis owing through an aisha, hoizonal dt Messurerentst the A end igicae ‘emperature of 340°K, a pressure of 105 KPa an. selcity of 7514. At the Bend of the duct he temperature bs 300°K. the pressure fs 90 KPa, an the velit i 305 ms ‘Whats the low dzecton, A 10 Bor Bw A? £8462 Tavs hg/so helium at $00 KPa and SUK enter an mulated device where the Work performed i 0, The id cvdes nto twa equal streams leaving the deve, both st TOO KPuan one. 85°C and the otherat an unknos temperature Nesecting changes in kinetic and potential encries, what sth ei tomperature ofthe second sear? it oss far the device to opens? £863 Steam flows steadily through a turbine from inlet conditions of $ MPa, 200°C, and neligile velocity to ent coaitions of LOO kPa, saturated vapor and a veloity of (D0 fs Hearst. 25 bh, fomthe turbine casing esursat an average trmperature of 10°C: Determine the work per unit mas (8) the rate of entopy production in the Tusine per unt mass of team fowin Urouah the Turbine ‘864 Consider the turbinein Probl 8.6: etthecontoalso envelop par ofthe power pla ‘which sata semperaturof 17°C, What isthe entapy procketon per unt massof Sam inthe conto volume under this circumstance? 8.65 A compresioeecives0.2 ms ofairat 27°C and 100 kPaend compressesit 0 700 KP She 26": Hest ss per unit ms rom the compressor sta a 100°C 5201.) 86270° ewarrea a yenraory Determine the power require, necting changes in kinetic and potential enties,(b) Determine the entopypradoction forthe compressor, {8.66 A.0.5-m eank sina evacuated A vale connectngittoa very lage supeyofseam 2150 KPa and 300°C apened, and seam flows ito the tank unl the pressure is $00) Ps. ithe process abt, determine (a he nal sea temperate nthe tank (8) {he entopy produced in the tank 8.67 4.0.20 ankistobe charged with air from alargesupply hat sat 320°K and 1000 kPa “The tank scharged aiakaially ul the pressure in the tank equals tha ofthe sup, Batennine (a) the temperature of the air in the tank (6) the entropy produced inthe proces PROBLEMS (English Units) “81 Oxygenis neatedat const volume fom 50 psa and 100°F to SO0°F: Determine de change of entrap per unit mass. +82 ici enol at constant pressure fFom $00°F to 100°F, Determine the change of entropy per unit mas, *R3 A threprocescple operates with [Tb oF ae an the fllowing cyte: p, = 18 psa, T,~ SO0"R, process 1-2, 1° Cheating: p,= 6 pia process 2-3, sentopic expan Sioa: )™ 13 sa, T,~ LOR, process ¥1,p~ Coline Determine the Fs diagram sd te cele thermal eiciency “RA Which eee, inated below, ste higher thermal ficiency? 8S Airiscontainedin a Lf tan a 2000 psia and 200°F. Ini cooled by the suroundines ntl traches the rerrounding temperature Of 20°F. Conadering the tank ad the ‘rounding san soled system, what she net entropy change? PRomEMS fogith Units) 274 +84 Air iconianod in 9 [0-8 wank at 75°F and 25 psa, Pade work i ated, 24 Rlbt forae foe 100 revolutions. 19.1 Bw of heats emoved, determine the Enal tempera fursand change of enzopy af the ae +8712 hme steam is trotted from 1000 psi and 00°F to 100 psa determine the change of entropy. °88 Scam condensteat 250 pia levesa heat-exchanger trap nd ows.at 3,000 Ibe sh ajacen las tank, Some of the condensate dase fo steam a 25 psa, andthe ‘emaining condensiispurped back othe bor There sno subcooling. Determine ‘hone entropy ohana. +89 chemical proces rai SUDU lb/hr of ho wera 80°F and 28 psa. Steam is Sslablo at (00 psa and 90% quality. and waters avaible at 10 pia and 70°F. The Steam and water are mised in an adisbatc chamber, wit the hot wate exiting. Deter ‘mine the net etropy change 8.10 An isothermal compressor consumes 10 fp while compressing ai from py f0 pat a ‘constant tamporture of 77-F The surroundings are at temperate of 38°F. Date ‘rine (the rae of extropy’ change ofthe ars (9) the rate a entzopy change of the sutoundings| *R.LT A consant- pressure sgstem contain Ibm of eam as asaurte guid at 50 pit The {sstem receives 200 Bt of eat fom a reser a: 1090". Considering thesyser and the reservoir as an slated system, clcuute he entropy production, ¥812 A Carnot eye reeves 1000 Bao heat whl operating between temperaturelimitsof 1000°R and S0°R. Determine the entropy change during best akon. +813 Inahome eget, $ fom tin of 12 enters tbe evaporatorcolasasaturatdliquid at 357 pia und leaves av strated vapor atthe same pressure. The refgeated space ismaintained ata constant teniperature of 40°F, Determine te rate entopy change ofthe refrigerant and ofthe rerigerate space, 8:14 stom radiator hasa volume of 2.010 and contains saturated vapor a 147 psa. Asa result offhet ranferto the rom. the stem condenses and the nal temperature af the Tigi before the steam tap opens is 1 20°F. Determine te eneopy change ote steam Foe this process +8, Anudiabutic nk contains 0.7Stbu ofsturte gui waterand025bmofsatarated ‘ex at 147 psia Ao eletric heater is inserted i the ank and cured on ws all the Tigi vaporizes Deterine the final seam presire andthe enrapy change ofthe 8.6 Am adiabatic tank is paronad into oo eausl volumes, one containg 0.5 tbm of ‘tured ain at 30 psa andthe other oly evacuated. Te partion s removed, ‘Whats the entropy change ofthe team? 4,17 Aninslated R12 somsiner develops ea, The elrgeran belo thelesk sat 70 pia land 60". Determine the mas of eeltigrantremaiting whes the pressures 30 sa S88 4 10-R° tank containing steam at 160 psa and $50°Fisconnected vialineand valve ‘apistoncinder. The valveconnecting the tank othe piston opened an the piston Fest constant pressure of (4.7 psia. This proces cantinucs unt the tank pressure feachos {7 put. Assume the process te reversible, Determine (a) the Bal steam ‘Sate nthe tank (tbe Wark done in the piston-yinder. 449 Anaciabotc heat exchanger esnes 300 Iban of ature tea on the hel ide 425 psa, which condenses tow saturaed guid. Water enes the tubes at 80°F andam leaves at 95°F, Determine the entopy change for each substance andthe eattopy production *8.20 A dreevcontat heat exchanger eines saturated steam at 7S psa and 2500 bin ‘otwvaver a 78 pia and 70°F Water leaves the hea exchange ss asaturtedguidat 73 a, Determine the enrony production. "8.21 4.10 Tom copper ings, ~ 1.10 Bt/TbmeF, is heated to 900°F and dropped into an eiabae tank holding (25 bm of water, nil at 70°F. Determine the entopy thange for the water and forthe copper sd the otal entropy production *822 Aninilated piston ofa enters the evaporator a 110"Fana atmand is cooled a constant presure. 7p 77°F an p=] ate. Detersine he avalabiity ‘changes ofboth te alr nd the regent, and the ieversibity rae. 9.32 Methane entre a compressor with steady volumeti ow rate of 80 /min at 100°F find 30 pa I compresecs to 45 pia thermal. Ty 77°F and py= 187 pa Determine the Ret nd work availa anser ates sod the ireversiiity Thiscan be '6S°F, Dee ¥9.38 A manufacturing proces requires 800 gpm of water a 175°F and | ‘bisina! by mining dry saturated steam a 1 atm with subcooed water moms (ENGUSH UNIT) 313 rine for Ty = 77°Fand p= | stn a) he water and steam ow rats; (0) tbe ever ty ofthe proces 9.6 & manufacturing proces requis steam at 400 psia and 700°F Saum is avalable st another action at 1500 pia and 900"F A suggestion is made to tvotethesteam 10 ‘he desired prewure and thes coolit ta the desired empertare throws est anaes ‘he sueroundings, which ae at 100°F. Determine fr T= 77°F andp,= 18.7 pia the total availablity destruction for the proces per unit mass. °9.35 Referring to Problem *9.34, another engines sugess expanding the team through an iabatc turbine co the desired pressure and then heating or cooling the stem tothe esd femperture, Investigate the availabilty estsucton in this scenario. Whit +9.36 Twente lbmsec of ai enters an adiabatic turbine at 900°F ang 90 pia with » selocty of 150 fer and exis at 440"F and 1S psi with velocity of 30 fsee Deer- mine for Ty= 77°F and fy ~ 14.7 pia (a) the power produce (b) the fenton and Seconds efiiecies, *9:37 Thiny-ive Ibm sec ofr enters an adiabatic compressor at 17.4 psi ad 68°F wits 2 Selocty of 180 fisee and exits at $8 psia and 320°F with a velocity of 250 Rise T= 17°F and p= 14 psa Determine the power sequie, the change of availa {ny and the ssconela efficiency 9.38 & compressor reseves 11 Ibon/see of ae at 147 psi and 100°F and compresses ito 120 piaand 350°F- Heat anser ror the compressa othe surouncngs i450 kW Determine the compresor power and its econ efficiency if Ty 7?"Fand Py ra pa #99 104 tank cootins dry saturate seu at 1S psa eats aed until he presure reaches 30 psi. For T,= 40°F determine the avallble portion of the heat ade. 3.40 A boiler voces dy strate steam at SO psa, The frac as ener the ube bank a2 temperature of 2000"F, leaves at a temperature of $00"F, and has an average ‘pei eat e, 0.28 Buuflbav over this temperature ange. Neslzcing heat loses om the ble and forthe wate entering te boiler asa saturated liquid with rte (of 1% 10 Ibm, determin or T, = 70°F(a)the eat vansfr(b)thelessvaiabie rey ofthe es: (0) the ain of available energy of te stam: 2) the entropy produc *9A1 A tank contains water vaporate pressure of psa anda emperaure of210°F, Heatis ‘added tothe water vapor wal te pressures wile, Te lowest avalae temperature 1S 60°F. Find the availabe potion ofthe heat aed 9.42 Five Ibm of aris cote from 30 psi and 40°F to 40°F at constant volume, All the heat isejsted othe suroundings a 25°F, Delrminetheavalable portion ofthe het emoved. Draw ¢T-sdggram and abe! the avilable ang unavailable portions of 2 ener reed 99443 Stoum enersa turbine a 900 psia and 900" and exits at pia with x quality of 89%. “The ow rates 20 Tose, Determine (a) the fos of availabe energy; (0) the avalabe pei entering the turbine (the availabe portion ofthe steam ening as turbine (3) ‘he ves work 6) the secoaddaweficency. Ty = 337° 944 An sictubineeceivesairt 120 psia and 1500" F The sir leaves the turbine at 1S sis fnd730"F- Ty = 380° R- Deseret alle energy eneriny he carbine) he ty change across the turbine (6) the reversible work. (2).a4 (CHAPTER 8 / AVAILABLITY ANALYSS COMPUTER PROBLEMS (C34 Air is compres isenropialy in a compreir from almosphene condons of {00 kPa and i K to varios dschatg pesres Deveop a computer model fo the omprsor io determine the cane oat ofthe ai for dicbrge presses of 50 Ka 1 Mb, $ MPa and 10 MPa. You may ve he TK Soler model ATR TR (C22 turbine wihan seotopiceiciene of 2% adataticalexpandsteam, exhausting it tosconener where he presses pia. Develop mala forthe tine to compete ‘echang of vali and avaible energy acrosthe turbine forte allowing stam inc conditions [ON and 100 pi, 300 pa, 500 pe 1000 pa, 1S00 pom and 2000 ps; 1000 pia en S0°F, 600°, 70°F, 00°F. S10"F, and ODE. Assume ‘rg= T0-R You may use he TR Soiee model STMCVCLE Te (23 A telngeration somoresoraiabtcaly compress surat R 12 vapor fom aniatet reste of 300 KPa fo satya dsehagepresures Develo a compre mde ‘it ascondaw eficience of 80% 85% and SOW ad determine the ange vale Shilo Uschage resus rom 600 Kho 120 Pa isrerentsoF100 KPa Aso, compte the vali change for adscharg pressure of #30 KPa ane pressures Sangin rom 150 KPa 40 KP in SD-Pa increments, You may wa the compresor ‘noel om RIZCYCLE TK 10 Thermodynamic Relationships “The problems in previous chapters were based on the assumption that the property values forthe various substances were available, The specific heats, the tables of properties and so on ll have to be determined from experimental data. The ques- tion arises as to hav, from an experiment, the necessary properties cam be deter- ‘mined. Experimenters cannot blindly set up an experiment ané hope to achieve ‘meaningful results, They must know what ta ary in theexperimsent and what to hold Constant. They are further limited in that only four properties are measurable: m= perature, pessute, volume, and mass. All emaining properties must be calculated from these four or from changes these properties undergo under certain conditions Tnorder to achieve the desirable result ofteststhat are useful, experimenters must be theoreticians as well. They must develop a mathematical model for thermods namic properties and use his in determining the functional relationship between the four properties Thisis the purpose ofthe chapter: to show you the method used and toillustate how properties may be determined. One may have a good model of ‘substance, butt isonly a mathematicl model, not thesubstanceitse Thisistrue of all sciences that predict sytem behaviors. Tn this chapter you will + Physically and mathematically intorpet dtfrontae: ‘Apply mathematical analysis to equations of sate ‘© Learn of Maxwell’ telations and their usefulness 318a4 (CHAPTER 8 / AVAILABLITY ANALYSS COMPUTER PROBLEMS (C34 Air is compres isenropialy in a compreir from almosphene condons of {00 kPa and i K to varios dschatg pesres Deveop a computer model fo the omprsor io determine the cane oat ofthe ai for dicbrge presses of 50 Ka 1 Mb, $ MPa and 10 MPa. You may ve he TK Soler model ATR TR (C22 turbine wihan seotopiceiciene of 2% adataticalexpandsteam, exhausting it tosconener where he presses pia. Develop mala forthe tine to compete ‘echang of vali and avaible energy acrosthe turbine forte allowing stam inc conditions [ON and 100 pi, 300 pa, 500 pe 1000 pa, 1S00 pom and 2000 ps; 1000 pia en S0°F, 600°, 70°F, 00°F. S10"F, and ODE. Assume ‘rg= T0-R You may use he TR Soiee model STMCVCLE Te (23 A telngeration somoresoraiabtcaly compress surat R 12 vapor fom aniatet reste of 300 KPa fo satya dsehagepresures Develo a compre mde ‘it ascondaw eficience of 80% 85% and SOW ad determine the ange vale Shilo Uschage resus rom 600 Kho 120 Pa isrerentsoF100 KPa Aso, compte the vali change for adscharg pressure of #30 KPa ane pressures Sangin rom 150 KPa 40 KP in SD-Pa increments, You may wa the compresor ‘noel om RIZCYCLE TK 10 Thermodynamic Relationships “The problems in previous chapters were based on the assumption that the property values forthe various substances were available, The specific heats, the tables of properties and so on ll have to be determined from experimental data. The ques- tion arises as to hav, from an experiment, the necessary properties cam be deter- ‘mined. Experimenters cannot blindly set up an experiment ané hope to achieve ‘meaningful results, They must know what ta ary in theexperimsent and what to hold Constant. They are further limited in that only four properties are measurable: m= perature, pessute, volume, and mass. All emaining properties must be calculated from these four or from changes these properties undergo under certain conditions Tnorder to achieve the desirable result ofteststhat are useful, experimenters must be theoreticians as well. They must develop a mathematical model for thermods namic properties and use his in determining the functional relationship between the four properties Thisis the purpose ofthe chapter: to show you the method used and toillustate how properties may be determined. One may have a good model of ‘substance, butt isonly a mathematicl model, not thesubstanceitse Thisistrue of all sciences that predict sytem behaviors. Tn this chapter you will + Physically and mathematically intorpet dtfrontae: ‘Apply mathematical analysis to equations of sate ‘© Learn of Maxwell’ telations and their usefulness 318316 CHAPTER 10//THERMOOYNAMIC RELATIONSHIS ‘¢ Develop adeeper understanding of variations in emthalpy, internal energy, and specitic heats ‘Discover how tables of properties are create. 10.1 INTERPRETING DIFFERENTIALS AND PARTIAL DERIVATIVES ‘To develop 2 mode! we must first understand gifferential equations and partial derivatives. Consider Z'= fUX, Y); then 82) ay 4 (2 (Gx), °C), con where dZ:i the total diferential: (7 /2X), ell us how Z varies with respect to Nat constant ¥ through a dilferential distance ¥. The second term, (32/37), shows how Z varies with respect to Yat constant X through a differential distance d¥, The ‘sum of both terms tells how a2 varies overall If 7 is assumed to be @ continuous funetion with continuous derivatives, then PZ a vay” avax a. (02) Equation (10.2) s an important relationship and is valid for exact differentials, liferenials that are point, not path, functions. This is true of properties, which {epend only onthe system state, but it snot tue ofthe inexact differentials, heat and work. To illustrate the inexact differential, consider the dlleretial of mechanical work, 6H’= pd¥’ Letusassume momentarily that Works an exact dierential, Then oY) aw (or), ( ‘The fst era onthe ight hand side eo because no work i accomplished at constant volume: this tells us, then, thatthe only work is work at constant pressure ‘This, obviously, is not true, and the hypothesis is invalid Physical Interpretation of Partial Derivatives Before we continue with the mathematical development of our thermodynamic ‘model, let us frst consider the physical significance of the patil derivative und how ‘these derivatives may be used in developing a thermodynamic surface. The impor- tance of understanding the diference between independent and dependent variables isa key co the understanding of the mathematical model. Any two variables are ‘independent ifone may beheld constant while the ther is varied, The changing of fone variable will not change the other variable, thus demonstrating their independ- 10.1 INTERPRETING OFFERENTIALS AND PARTIAL DERWATIVES 317 i Figure 104A set of three independent variables, with one ‘tying wile sno remain constant ‘eace from one anther. Figure 10.1 showsa set of three independent variables, each of which may be varied while the other two remain constant, ‘When 2, ¥, and 7 are used to describe some surface functional relationships “developed between the variables, and the concept of Gependence and independence appears. Let these variables desribe a sphere of radius; then O44 eR? (103) ‘An octant of the sphere is shown in Figure 10.2, and the lines on the surface demon ‘trate how two variables change while the third is held constant (On the surface only two variables may be independent; the third is dependent For any two pointe X, and Y, within the domain af X24 Y?-< 3, there e only single value of Z cal it 2, such that the point at (X,Y, 2,) will be om the surface escribed by equation 10.3, Atany other value the point, o state, will not be on the30 CHAPTER 10 / THERMODYNAMIC RELATIONS Figure 102 The vasation of two vas y bes ton sth the thi dependent, keeping the ine Sed Sn the sate a justice. Thisisshown mathematically by sovingequation (10.3 for ny variable, a aaa yay (104) Since R isa constant, this may be written as Z-AKY) ny giro usrauon cate proeton ofcuesalanda2inthe XZand ZY ane, 102 AN IMPORTANT RELATIONSMP 319 Hence, we get equation (10.1), ‘The partial derivatives are eraphically shown ia Figure 10:3, The equilinsum surfaces used in the previous chapters are thermodynamic surfaces. We will beable to develop the mathematical tools used in making these surfaces. The steam tables and other tables of propertis rely on these techniques it their development 10.2 AN IMPORTANT RELATIONSHIP “Another mathematical selationship between derivatives may be developed 9s fol- ows, Let us consider three variables, X, ¥, and 2, and suppose thet Z- AK Ge) eG but che relationship may also be written as Y=/UZ) a av ay-(2) ar+(Z) ae a2 and singin eon 18 or (5),0°~ (22), Ge), 2 Ga), Coie (2). @)lol@(2),G,Je 9 Since Nand are independent variables, any values may be assigned 10 them and ‘equation (10,7) willbe valid. Let X= const; then d= 0, G5), then a er 088) (1066) Solving for dZ, (108)320 CHAPTER 10 /THERMODYNARN RELATIONSHIPS 09) Equation (10.9) proves that pantal derivatives may be inverted, IF Ys held constant isequation (103) hen (Go),* (32), (9),-° com If we multiply equation (10.10) by (9X/2Y}g, (31), Ge), (9), 2), @),-° but the fist teem is equal to one, by equation (10.8), yielding 2,4). ary Equation (10.11) is very important and willbe used later 10.3 APPLICATION OF MATHEMATICAL METHODS TO ‘THERMODYNAMIC RELATIONS. “The fist law for a closed system om a unit mass basis is bq™ d+ p do 0.2) the process is reversible, bo=Tds hence du=Tds~pdo (10.13) Also, dhe du+ pdo+vdp thm Tash dp (014 ‘Two other thermodynamic relationships that are frequently used are the Helmbokte function, a, andthe Gibbs function, g, Written of a unit mass basis, anunTs 10.15) gehoTs (10.16) ‘Taking the derivative of equation (10,15) yields da=du-Tds~ sat 10.3 APPUCATION OF MATHEMATICAL METHODS TO THEAMODYNAWIC RELATIONS 321 bot, feom equation (10.13), du T dsp de hence da=—pde~saT 0.7) Ad taking the derivative of equation (10.16) yi dg=dh—Tis~saT but dh-Tds=edp hence dp~ sav (ogy Equations (10.13) (10,14), (10.17), and (10.18) are ofthe same general form. Ineach case ve a dealing witha thermodynamic property expressed asa funesion of other thermody nant properties, Under the constraint ofthe state postulate with 2 single fquasistatie work mode, any property ean be expresed as the function of two other properties, provided these properties are independent. For example, considering ‘equation (10.13), we can write then (10.19) ‘Comparing equation (10.19) and (10.13) yields a ae : (2), ---@), (009 Reationships between the other fees may be deeoped fom equations (hots, 07) ano 1018) nasa manner. They ate summaries alow )-r Gi), (a2222, CHAPTER 10 / HeMMOOMNANNC RELATIONSHIPS 10.4 MAXWELL'S RELATIONS Another group of relations, called Maxwell's relarions, may be developed im the following manner. Differentiating equation (10.20), hence (i), --(@). 020 Equation (10.22) is one Maxwell relation; the others may be derived in a similar manner, and the following will result @.-@), (,-(), vom G),--G), 1t should be recognized that this is not a complete listing, but a function of equations (10.13), (10.14), (10.17), and (10-18) more terms, sich as suriace work, were added to she es-law equation, chere would be more Maxwell relations, How «ver she ones listed in equation (10.23) wil be sufficient forthe applications in this text Should others be needed, they may readily be developed, 10.5 ECIFIC HEATS, ENTHALPY, AND INTERNAL ENERGY. ‘The specific heat at constant volume was developed by considering a constant volume process hence the fist law is writen as 8g = d= c, dT, and c, is defied (52), 59), uea9 105 SPECIAC HEATS,ENTHALEY, AND TERNAL ENERGY 323 Ina similar manner fora constant-pressure process. éy di "(89 (8), 9-H, com sispose 1 developanexpresson arent entra enti ermsofthe {pose heats and empeatte and pesur. Ths the inet oe chapter, owe the measurable proper to obaianonmeasrabeproperics Shee can be expresed 5 = (7,2) au~ (24) ars (%) a (025 AT. andc,isdefined Tas~ dut pao For P= Cit fllows that (2) -r( : ()-r( and equation (10.26) becomes . 22) — oa 10.29 aumcart[r(2) -o]a ( av=(22) ar+(2) os rave use a Maxwell relation, ),- 0.32)324 CHAPTER 10 / THERMOOYUANN RELATIONSHPS Substituting equation (10.32) into equation (10.30) yields aome[e-(3) Ja ‘The functional variables were chosen in each case so that the frst term woul be the speciic heat. All that is needed to integrate equation (10.33)is «correlation between T, p,and e (1033) Example 10.1 Assunme tht ait hasan equation of state p(e~ 8) = RT. Assuming the specific heats are known, determine an expression forthe change inthe speifc internal eneray. Solution Given: Find: Expression for the change in the g's specific internal energy: Analysis: The general expression forthe change of specific internal energy for @ Simple compressible substance is siven by equation (10.29), vol) Solve the equation of state for p/ Gs equation of sate ay R Take the derivative of the equation with respect 10 temperature, holding specific volume cosstant TepseN, pW). 4 r Solving for Tlap/eT) yields Tapia and substituting into equation (10.29) yields du c,dT+[p~pldo=e, dT Comments The gas equation of state in this example is that of an ideal gas, the Causius equation of state: For more complicated equations of state, this simpliica- tion will not occur a Entropy and Specific Heat Relationship “The equation for the chnuge Fenty maybe Rou inne following manner. The res lead toa very important thermodynamic relationship between the specie heat at constan volume and constant pressure 105 SECC HEAT, EUTALEY, AND TERNAL ERGY 325 Since s can be expressed as s=/(T,P), as as ar=($E) ar+(B) ae Using equation (10.25) this becomes ar, (2 ane, E+ (2) ap Using a Maxwell relation from equation (10.23), (Ge), (9034) 035) We now let sf) o-(&)+(),« ane 4(%) T 20) (10.35) Equations (10.35) and (10,36) both express the change of entropy, but they use diferent specific heats. Again, an equation ofstateis needed to determine the partial erivatves Specific Heat Difference Another relationship denoting the difference in specific heats may be found i the following manner, Let ws equate equations (10.35) and (10.36) ah =(82) somesth (22) Tlev/9T), dp + Teap/aT), de ara HEBD MePHM He yay saa T= Tn ar-(22) ae+( 2) 0 comp ‘We equate the coeficients of dp or dein equations (10.37) and (10.38), The following326 CHAPTER 10,/THERMCOYNAMIC RELATIONSMS is found by equating the coecients of omen) 78), (é#), (FF From equation (10.11), we may write forp, ». and T ),@).8),-— 7) (2), wa Sbstiaing equation (1040) ato equation (10.39), o-en-r(2) (22) (22) onsnr (54) (55) (2), ---9(22) (2) a Tce conclusions flow fom applying experimental bsenatios to eution (10.41), sees ees 1. Since (90/97), is very small for liquids and solids, the difference between cy and ¢, is essentially zero: only one specific heat for liquid or solid is usually tabulated with designation of eonstant pressure of constant volume. 2. As T-approaches 2er, ¢, approaches ¢,. 3. Forall known substances (3p/@2), <0, and (20/3T)3> 0 all the time; hence (10.39) from whic incompressible Substances ‘Very often its possible 1 consider solids and liquids as incompressible substances. When tis isthe case, simplifications in the expressions for internal energy, enthalpy, and entropy are possible. For an incompressible substance the total sind partial erivatives of specific volume are zero. This allows great simplification in some property equations of state. Thus, the difference between specific heats (equation [10.41)) 6 2en0 anc Gear’ Furthermore, the expression forthe change of internal energy (equation [10.29)) 108 CLAPEYRON EQUATION 327 ‘becomes dum cd? The expression forthe change of enthalpy (equation (10.33) becomes dh edT + ody Aya hy yt Fels) and the expression forthe change of entropy (equation [10.36) becomes aT anced ropes 8 ee “The specific heats of mos solids and liquids vary Tineanly with ermperata previous equations may be readily evaluated the 10.6 CLAPEYRON EQUATION Its possible to predict values of enthalpy for changes in phase ofa substance in thermodynamic equilibrium. By equilibrium we mean that the system isin mechan jeal equilibrium (both phases are atthe same pressure) and in thermal equilibivm (oth phases are atthe same temperature). There isa direct correlation between the enthalpy change in vaporization and the volume change in vaporization, ‘The relationship that we want is (9h /),, but enthalpy cannot be calculated, so ),-@),(, and from equation (10.21) ~ (2) 0) os Fortunately, in the saturated region a constant pressure process is also a constant _— @)-()-@). aan ‘rom equation (1023).8 ‘CHAPTER 10 / THERMODTIUNIC RELATIONS Since the pressure isa function only of temperature when two phases are present (soe Figure 4.5), the partial derivative may be written as a total derivative in this, saturated region. Equation (10.42) becomes an eo (@),-7() eo Denoting the change ofa property from a saturated liquid ta saturated vapor phase asf, equation (10.48) becomes s-r(8) : nynear() 04 Equation (10.45), whichis the Clapeyron equation, enables us to determine the change in emthelpy during a phase change by measuring the volume change, the temperature, and the lope ofthe vapor pressurecurve.Itheassumption smade that the specific yolume of the vapor is euch larger than that ofthe liquid and if we ‘employ the ideal-gas law to determine the specific volume ofthe vapor, the enthalpy of vaporization may be readily calculated. Let us assume that 15 aed yet 5 then Rr dp ip Ae (oa) tga aaa (10a caution (1047 singe, the allowing ress Inp=—hgi(A7)-+ conan ofitepaion np at air (vos) Where 4 and B are constants, Equation (10.48) is commonly used to represent the ‘relationship between saturated temperature and pressure fora substance. I suggests that ploting In p versus L/T wil pve a straight line 1046 CLAPEWON EQUATION 329, Example 10.2 [Determine the presure of saturated steam at 40°C if at 35°C the pressure is 5.628 kPa, the enthalpy of vaporization is 2418.6 kl /kg, and the specife volume is 25.22 mk. Solution Find: The pressure of saturated steam, knowing the temper other proper ties ata cifferent state Given: Steam properties at an adjacent state Assumptions 1. The enthalpy of vaporization is essentially constant between the 10 states 2. The specie volume of the liquid is much ess than that of the vapor and may be neglected. 5, Theideal-gas law may be employed to determine the specific vlume ofthe vapor. Analysis: "The Clapeyron equation provides us with the means to determine the pressure Integrate equation (10.47) between two states, yielding tn (2) -4e( a) ‘The salv of maybe looked up is he eal tbe orcleultedom he given data Th tr mthoa's preferable Rl vay beste of non elas es, ew DDL _ 25.22 fh S628 KN) 7 GUB°K) 0.46 kd hse Substituting into the previous equation yietds u(B) = Eta (tt) 7.) ~ Oa6 RI TR \3OPR— 31°K w() tnd solving forthe pressure p, yields p:= 7.392 kPa ant “This corresponds very well with the saturated pressure at 40°C, found inthe steam table to be 7.389 KPa. Comment: Tse Clapeyron equation isa very powerful ool in determining proper ties of saturated pure substances Its usefulness decreases at states near the critical State, as the assumption concerning the iferences in specific wee i ges valid. *330 (CHAPTER 10 /THERMODYNARIE RELATIONSHPS Example 10.3 Use equation (10.48) to develop an equation to predict the pressure of saturated steam ata given temperature between 100°C and 200°C. Use TK Solver to caleulate the values of 4 and B. Compare the esults for 150°C with the steam tables. Solution Given: Steam pressure and temperature at 100°C and 200°C from steam tables. ‘Find: The values ofthe constants 4 and B in equation (10.48) for saturated steam between 100°C and 200°C. Assumptions: 1. The enthalpy of vaporization is essentially constant. 2. The specific volume of the liquid is much less than that of the vapor. 3. Theideal-gaslaw may beemployed to determine the specific volume ofthe vapor. Analysis Using'TK Sotver, enter equstion (10.48) swe in the Rule Sheet, once for feach of the two data points, Enter the saturated temperatures and pressures in the Role Sheet, euess values for 4 and B, and solve. {Wh the values ford and 2 determined, enter 140°C (423.15°R) and solve for the saturated pressure FI 1077 IMPORTANT PHYSICAL COEFFICENTS 331 ‘This compares well withthe value i the steam tables at 150°C of 476.3 kPa, Comments: 1. The equation predicted the saturation pressure at 150°C with an securacy of about 2%, 2. Attempting 10 use the equation over a wider range Would resutin greater errors, since the assumptions made would be les vali = 10.7 IMPORTANT PHYSICAL COEFFICIENTS Several other important coeficiens are used to determine actual properties of = substance. From knowledge ofthe coeficient, property changes may be determined, Let us consider that ¥”= f(T, p); then a aoe o-() ro). We divide each partial derivative by V, which results in the following coeficients oo 4(2), =332 CMPTE 10 /THERMOOYNAMEE RELATIONSHIPS and Bs 4 (an 75), (1050) ‘where isthe coefficient of thermal expansion and fis the coefficient of isothermal compressibility. The negative sign is included in equation (10.50) because the volume decreases wit increasing pressure, and vice vers, so the partial derivative i aways negative and the minus sign allows always to be postive, The reciprocal of the isothermal compressibility isthe ieuhermal bull modulus, By’ (2 3,=-r(2) cost) ‘The difference berwoon the spociic heats may be expressed in teems of these coefficients. By equation (10.41), onon-1(F) (8), but and ve-() Hence, Thee c= oe (052) ‘The change in entropy at constant temperature may aso be found when entropy Js considered as a function of tempera -(2) oo wre G)-G ~~ (70.583) 10.7 WaPORTANE PHYSICAL coEFRCINTS 333, and mae (4:7 5p als — Pe (25a) “Thus, by knowing tabulated coefcients we can caleulate the propesty change of certain systems, For instance, the Handbook of Chemistry and Physieslist these ard bother coefcients for a great variety of substances “The homework problems atthe end ofthe chapter ilustate some typical cases ‘where the coefcients may be calculated ifan equation of sate i known, as inthe ase of gases. The idel-as lw wil yield ouch simplifed results, but these results ‘canbe helpful in confeming your understanding of the meaning ofthe various coei- Joule-Thomson Coefficient 2), wo dh=Tdst edo ss.0 (Gere), av-r(2) sre7(2) ove ds a7) For constant 7, dT = 0.336 ‘CHAPTER 10 /THERMODYNARNCAELATIONSHPS ah n(28 (),-7G),** i) From exuation (10.1) fr b= f(T) (80) (or) (ahy @),@),@),-— ar (2), 10s and ak () wos “Therefore, we substitute equations (10.32) and (10.58) into equation (10.57) 1 (a 2), (0035 pan fer( a @ aX, Foran deal gas, = 0, but that isnota necessary and sulfcient condition thatthe gus is ideal. Remember, at the inversion temperature, j= 0 also, To illustate why the Joule-Thomson cocficient changes sigh, we substitute i= w po into equation (10.59) sb), CP) vos) “The frst term in the rackets denotes the deviation from Joue's law, which states thet ‘the internal energy is @ function only of tempercture. On expansion, there is an increase in the molecular potential energy, and hence (2u/9p}yis negative. This results in a postive and a temperature decrease. The second term in the brackers indicates the deviation from Boyle's Ia (that v varies inversely with p fora tea zis For most gisest low temperaiuresiand pressures, (72) 9p; is negative; however it changes sgn at higher temperstures on presses, Figure 104 lusiratesthe plot of on the 7-pand Ts diagrams, Lines ofeonstant enthalpy are also note. 118 REDUCED COORDINATES FOR VAN DER WAALS EQUATION OF STATE 235, Figure 104 (a) T-pdagram showing ihe locusof pointory = 0.(0)A Tigram Showing the lows of pots for =O. 10.8 REDUCED COORDINATES FOR VAN DER WAALS EQUATION OF STATE In Chapter $ we used a generalized compressibility crt for gases to determine the deviation from the ideal-gas equation of stat. Because Z= po/RT = | foran ideal 85, use ofthe generalized compressibility chart enabled us to use one chart forall sacs in Chapter § ‘Why isthisso? The van der Waals equation of state will demonstrate that the use ofreduced coordinates leads oan equation ofstate in terms ofthese coordinaes, The constants forthe various gases are eliminated, The van der Waals equation of state is _ er 3 P 7 oon Figure 10.5 shows p- diagram with a plot of isotherms fora typical pure substance “The erieal isotherm is of importance. Examination of the experimental data has shovin that atleast the fest two derivatives are zero atthe eiical point: ), (3), [equations (10.64) and (10.65) are applied to equation (10.63), we may determine (1064) and 065)336 CHAPTER 10 / THERMODYNAMIC RELATIONSHIPS Figure 1035 A diagram fra typical pure sub- secs the critical properties from the van der Waals equation: (ns (0s a= Meq— 0» (106 Solving equations (10.67) and (10.68) fro yields =3 (2069) ing this in equation (10.67) reutsin te r=, (10:29) Substitution into equation (10.63) yes forthe citcl pressure nagty (om Using the critical properties, we rewrite the van der Waals equation of state with roatens (2) 337 reduced coordinates: Subst (10.72) Equation (10.72)illustrates that an equation of state may be expressed in terms ofthe ‘reduced coordinates and be applicable for any gas. Hewever, no substance obeys van ‘er Waals equation of state exactly, since it san approximation of actual gas behav CONCEPT QUESTIONS 1, What are the diferenoesbenncen parial and ordinary difereti? 2. Given that w= ux, 3), under what conditions is the pata derivative (@u/),.equsl aaa? 23, Fors wx, the pail derivative, u/s function of x? ‘function of one variable may be representa a (x) ad is derivative as dif Can the ththag— hia) + tl I) Using the equation of state for enthalpy of an ideal gas and that the enthalpy of the ‘water vapors essentially equal to the saturated vapor enthalpy’ atthe mixture tem360 CHAPTER 11 / NONREACTING IDEAL-GAS AND GASVAPOR MIXTURES perature yields Fig ™ hy a8 90°F = 1100.8 Bay/lbm ha = hy at 40°F = 1078.9 Beu/tbmn (= (39.81 tonv/miny0.24 Brujlbm-RY550 ~ 500°R) + (0.163 Iom/min)(L 100.8 ~ 1078.9 BrufTom) 72.9 +3.6= 476.5 Bru/min ° Comments: 1. The relative humidity decreases because the partial pressure to which theaircould be saturated with water vapor ineteases asthe temperature increase. 2, The water vapor conteibution to the heat fx is small unless a phase change 3. The substances need to be separated when finding the enthalpy differences, 2s ferent reference datumsare used in defining when the value ofenthalpyis2e0, Adiabatic Saturation ‘The adiabatic saturation proces isan important process in the study of air—water ‘vapor mixtures, In this proces, asthe mame implies, the mixture is saturated with ‘water vapor disbaticaly. To visualize thi, consider the schematic diagram in Figure 1110(2) An unsaturated (( < 100%) air~water vapor mixture enters an insulated uct. I the bottom ofthe duct lies water, which evaporates and becomes water vapor inthe mixture. Th heat from the vaporization must come ftom the enthalpy of the incoming mixture, Since enthalpy is @funetion of temperature, the temperature of the mixture decreases, I'he mixture and liquid wate are in contact for long enough, the mixture wil leave asa saturated mixture atthe adiabatic saturated temperature, For this tobe a steady-state problem, the changes in Kine and potential energies ‘must be zero, The water must be supplied at the adiabatic situation temperature, or ‘correction must be made for heating the liquid to the temperature. Since this is an pen system, the first law is igh ay + hy = Mgha + Mge a Og + (05 hy = ha, + hg Cha ~ hi) ha ha + Oth, ils T))+ 02th) The adiabatic saturation fempersture, Tb a funetion, then, ofthe let tempers ture, pressure, relative humidity, and exit pressure. Figure 11-10(b) illustrates the adiabatic saturation temperature on a T's diagram. (12) aahy hy) = 12 psvennoweren 361 a Ll non? gure 1.10 (a) An adiabatic saturation uni for stead ow.) ‘APs dagram llusrating the adiabatic satoraton temperature 11.3 PSYCHROMETER ‘To determine the relative humidity ofan air—water vapor mixture, psychrometer ses to thermometers. A cotton wiek saturated with water covers the bulb of one ‘The dry-bulb thermometer measures the temperature ofthe air-water vapor How. It the air- water vapor flow is not saturated, water will evaporate from the wick on the ‘wet bulb. The energy for this evaporation comes, in par, from the internal energy of | ‘the mercury in the thermometer, whieh then decreases, causing crop inthe temper- ture ofthe wet-bulb thermometer. Eventually a steady tate is reached in which the change of temperature ofthe air, water vapor, and thermometers 2270 with respact to time. This requires that the relative velocity between the air mixtore and the ‘wet-bulb thermometer be greater than 3.5 mys, minimizing the eflect of radiative heat transfer and making convective heat transfer a predominant mode. For air at atmospheric pressure, there is very ltl diference between the wet ‘bulb temperature and the adiabatic saturation temperature. This is not necessarily true at other pressures or for mixtures other than the ait-water vapor miature Several items afect the wel-bulb temperature reading: conduction along the362 [CHAPTER 11 /NONREACTING IDEALGAS AND GAS VABOR MOXTURES gure 11.11 (a) We-bull an dry-ball thermometers (b) Handheld sing pychrometr. thermometer stem, adiant heat transfer from the surroundings tothe wet bulb. anda ‘boundary layer between the wet bulb and the air, The adiabatic saturation tempers- tureisan equivalent temperature and not affected by these items. Thereason the wel land dry-bul temperatures determine the state of the mixtures not readily apparent ‘Two independent propertis are necessary forthe determination of the state. The dry-bulb temperature is one such propery. By knowing the wet-bulb temperature we nay determine the vapor pressure for the mixture, which combined with the static pressure, 1ypicaly atmosphere, defines the second property. Figure 11-11(a lus- trates a psyehrometer. Ina sing psychrometer, Figure 11.1|(b), the two bulbsare in casing and are whirled around to achieve the necessary relative velocity “The TK Solver model PSYCHRO.TK permits the convenient determination of the properties of air—water vapor mixtures. PSYCHRO2.TK analyzes processes of such mixtures, Wit the input of any two independent properties (dry-bulbtempera- tute, wet-bulb temperature, dew point, relative humidity, humidity ratio) all the ‘other propertie can be determined. When analyzing processes using PSYCHRO2.TK, the change in dy-bulb temperature, humidity ratio, or enthalpy canbe used as an input forthe second point. Example 11.7 Repeat Example 1,6 using PSYCHRO2TK to compute the relativehumidity ofthe 11 povenwoweTeR 363, Solution Given: The dry-bulb temperature and relative humidity of moist aie entering a ‘constant pressure heating duct and the exit dry-bulb temperature Find: The relative humidity of the exit ae, Sketch and Given Dara: See Figure 11.9. Assumptions: Same as for Example 11.6 Analysis: For the heating proces given, there will he no change in humidity ratio ‘between inlet and exit, Entering the piven temperatures and rcative humidity, and 2910 for the change in humidity ratio, PSYCHRO2 TK calculates the ext relative ‘bumidity Comments: 1. The exit relative humidity agrees closely with that calulated in Example 11.6 2, The change in enthalpy computed by PSYCHRO2,TK can be used te caleulae ‘the heat fux ofthe proces. a(CHAPTER 11 /NONREACTING IDEAL-GAS AND GAS'VAPOR WOKTURES CONCEPT QUESTIONS 1. Dsexbe mass factions and mole ston 2 Isit possible for the mass and le factions of « mixture of CO and; to be he same? why? 4. For an idee-gs minture the su of the mass Fretons i unity. 1 this also true for onside mistres? Why? Isa tistre of deal gates aio an ideal gas? Wy? Describe Dallon’ law of partial presure. Describe Atnagats aw of additive volumes Consider a gas mixture with several components, Which component will have the higher pal presure the one wth the Ingest numba of mos or with the retest mass? 8, A tank contsne two ideal gases. The tanks heated and the temperature and presur of the tank increase, Do the paral presures of each component increase and remain the same proportion? 9, plain how the intemal enevy change of a minture is termined. 1. Explain how entopy change of sntures determined fr adiabatic conditions and fo onaabatie conditions 1, Wht isthe dlifeence between dy ar and aumospheie ae? 12, Under what circumstances can the water vapor ns be teat as an del 935? 13, Desribe vapor pressure 14, What isthe diference between relative numidity and specie humiity? 15, Exgkin wet. and dry-bulh temperatures, 16, What she aaiabatie saturation tempore? 17. Explain the dew pot temperature 1B, inthesummera gles ofcoldwatrwil requetly have condensation on the outer suri, way? 19, Atwhat condition are the wet-and dull emperstres the same? ;OBLEMS (5!) 1.1 A.gaceous mixture haste Following vlumetic analysis, 309% CO 40%: Ns, 30% Determine (athe anelsison amas bass (0) the partial presur ofeachcomponentit| the total presse 100 KPa and the emperture is 32°C; the molecular weight of| the mixture 11.2 A gaseous mistare hash ellowing analysison amass ass: CO, 30%: 0s, 30% He, 2, N,, 20%. Fora total pressure snd temperature of 101 KP and 300°K, determine {a} the volumetric moll anal (6 the component pari passres (he mixture fas constant: (2) the mintae pect eats 113. Acubical tank, | mona side, containsa mstur of 1.8 kgf nitogen and2.8 kgotan Unknown gan entre prestre and terete are 250 xPa and 340°. Der ‘ine (a the molecular weight and gas constant ofthe unknovn gs; (6) the volume analysis roams gi) 365 114A mixture ofidel sass at 30°C and 200 kPa is composed af0.20 ke CO, 0.75 ks, and 0105 kg He, Determine the misture volume M15 Equal masesofnydrogen and oxygen are mixed. The ixtureismaintainedt 180 kPa and 28°C, Foreach component determi the volumetric ana and ite partial pres 1146 A 3a0'drum contsineamineureat 101 kPuand 35°C of metnancand dos oween ‘ona volumetric basis Determine the amount of oxygen that must beaded at 35°C 40 ‘hang the volumetric analysis to SO for each component. Determine also the ne mitre pressure 117A gaseous mixture of ropane nitrogen nd hydrogen has pr pressres o 83 KPa, 102 kPa, and 55 kPa. respectively. Deerine (a) the tlumeiic easy; (0) the araimetie (mas) analysis. 118 mixture of gases contains 208 NA O,, and 40%) CO, on a mass basi, The miacure posure and temperature are 150 KPa and 300°K (a) Coasiorthe mixture ‘behestedina 20-m? tank 1o 600°K: fin the heat equted. (6 Consider the inte to ‘efiowingseadiy at | hg rough a heat exchange uni the temperature is due: fd the Rea rate reque, 119 A ig insulated tank, 28 shown in Figure 1.4 is divided into two sections by & ‘membrane. One side contains 8 ky of rtrogen a 200 kPa and 320°K, and the other Side contuns 104g of liam at 300 KPa and 400°K. The membrave is remove, Determine a the miu temperature and pressure (6) the change ofentcop forthe system: (the change of intra ener of he sate 1.40 A rigid insulated tank shown in Fire 116, contains 0.28 m’ of nitogen and {hai of hydrogen, The presure and temperatute ofeach ps is 10 KPa nd 93°C. ‘The membrane separating the gees is removed. Desermine the encopy of mixing 1141 Funlene i stored in a Str spherical esol at 260°C and 2750 KPa. To pateet, aginst explosion, the ese isenclosed in another spherical vessel witha volume of 6 Titers ane led with trogen a 260°C ard 10.1 MPa. Te entire aterbly 5 rain tained 260°Cin a rsa, Thier veel ruptures. Determine the dna presse Uh) theentropy charge 142 An aie conditioning unit reccives an ai-water vapor mixture a 101 KPa, 38°C, aod 10% lave hums. Determine () the dew pot (b) the humidity rao: 6) te partial pressure of ar) the mass Faction of wate vapor. 113 An sir-water vapor mista at 158 Ps, 42°C, and Si lative uit is contained fina Lm tank The tak i cool to 214C. Determine (a the ens of water com dense (5) thepaial pressure of water por ntl othe il mintre pressure (2) the heat transced 114 Given for an air—water vapor misture that Ty = 40°C, Pg, = 300 KPa, and = 51% fn (a the dew points (the hamity Tato, |ILAS Gixen for an ar-water vapor mixtre that Ty = 70°C ad Pag = 200 KPa an, = 180 KPa, find (a) the dew pot (b} humic ato) relative hum 1.16 The mola analysis of 24s miata at 300°K and 100 kPa 65% Ns, 258% COs, ane 120, Determine (othe mass fraction ofeach component) parti pressute(0) ‘he vale seruied by 20 kg ofthe tare 1.17 A gas mistre has components withthe folowing mass rations 0% COs, 20% CO, ‘0d 30% He, The mixture temperature and pressure are S0°C and IS0KPa. Determine366 [CHAPTER 1) / NONREACTING 'DEALGAS AND GAS VAPOR RXTURES (a) the mote rsetons (b) the pl pressure ofeach component () the miatoe 3s 1148 A Sdliteriaakcontains0 6 kgafnitrogen and 0.6 ky ofatbon dioxide st 300°K. Heat {Stansted un the temperature ries to 00°K. Determine the entropy increase of thes 11.9 Anadiahaiccompresor eseves Zhg/sofa gas mintue and compresssitiom 280° Sun wPa to 20°K and $00 KPa The miatue’s mass factions ae SO% Ny, 3% CO, and 20% 0, Determine a) the power required: (b) she exttopy production 1120 A mixque of. kgmol of atrogn and D4 gino of ammonia scompcesed isother ‘uly fom S10" abd 100 KPa to 400 KPa. Detrine a) the work required () the Feat rants () the entropy production 1.21 A tucine receives 1S hg/of agus ature at 800 kPa and 100K and expands ition sae of 100 kPa sentria The nature oll analysis is 60% Ns, 20% COs, {Bnd 20% mater vapor. Determine (a) the ext emperature:(b) the power developed 1122 A mintue containing SO Ee and SON, on a masshasis enters nozzle at 480° K and SU kPa otha velo of SOs. Iveypandsisetopialy through the moze. Theeit ‘eloety om the nove is 300 m/s, Detenmine the ei temperature and pressure, 11.25 Aposmisture witha mola analysis of 60% Ny and 40% O, enters an iat compres. fob as L3 Kye 100 KPa, and 290°K, The dscharge pressure is $00 kPa, and the {Sscharge temperate ip 500°K, Determine (a) the second-iaw eiciency: (8) the poner: c) the entropy preduction, 1124 Twom? of 1 at 300°K and 100 kPa mixes adiabatically with 6 m?of gas 2at300°K, ind 250 Pa Determine (he inl pressure of te vate; (b) the eneopy change of each 218 1125 A quantity of neon, 05 ¥g at 20°C and 100 KP, scone in an adiabatic tank, ‘Another adiabatic tank contain 0,7 bg of eitrogen at 390°K and $00 KPa. A valve onneating the anks is opened an the pes achieve equilibrium. Determine} ech {a's volume; the final mixtre pressure (the entopy production, 1.26 The tanks in Problem 1.28 are aonadiabatc, andthe final mixture temperature is °K Determine (thea! pressure) the beat ans the entropy change of ‘ash component 11.27 Two bg of nitcopen st 67°C and 100 KPa min assay with) ss Blograms of upuen, (ese blogs of noe, bth of which ae arte same inkl conditions as the 24g of aitrogen, Detemaie te entropy production. 28 An aliabatictank hrs two compartments one containing? kxmol of carbon dioxide at SO0"K and 200 KPa and the other sonttning 2 kemol of mitogen at 420°K and 00a, The gases mix andJ00 kd ofeneryisaddedhy x restance eater Determine ia) the mixture final tmperature and presse: (B) te hae in avaiability() the iteveesibity of Ty~ 300°. 11.29 Two ke/s of helium sows seal ito an adishatic mixing chamber at 87°C and {00 KPa and misc with mitogen entringat 287°C and 400 kPa, The mintreeavesat $80 Pe with moll analysisof Hand SON, , Determine a) he temperature of Ate misturelavng he chamber; (b) he fate of entropy production, 1130 an inaustat proves eusics sintuze of ntogen and halen a 120 KPa. The ‘snc ncreated ty acabaticaly combining 3s of nittogen at 160 KPa and 310°K PROMLEMS freien Unis) 367 1.5 kale of Helium a 175 KPa and 415°K. The mitre les the chamber st 150 ka and i thot to 120 KPa, Determine () the femperture ofthe mintoe cxting te chamber ang exng the trong abe: (2 he ersop produstion aes ‘Sechamber a son he ting ae me 11.1 The temperature ofthe inside surfce of rooms exterior wali {S*C, while the ‘emperatureothe airin thecoom 23°C. Whatistha matimurs lave uy the sir in the room can have before condensation ceca? 11.32 Cold water fows through pipe he basement of s home at a semperatne of 12°C. “Tae ain the tusement hes temperature of 22°C, What the maximum relative bumidisy the ara have before condensation occs? 113 4 tot tank comains moa at a 27°C with hiya 0 0,08 SopogarWht ms mae mus be moved a owe te lab ae 1134 A oom oni atmophssial 25°C wihahuiiy sao of00! kv hes ‘What is the relative humidity and the dew point? caer 1138 a olume 6m far at 0X and 27°C with a eine hii of 5% ones other nil wat Cones A al peste ders conse Sonos 1136 inure often and wert 68°C and 100KPx tha moll ana 8% Ny tuasheaervruriceotacouten reser. Ata enmerdesthewete Sportscene! 1137 A pst ingen ume 073m? conta 48°, 120K 98 Goh aie tui Tes old Conan ol pes nei tcnpeoturs 0°: Wht eth wo ane et or 118 A ankconsinsaiisy 10°C S00KP, and rele hui, Henan ccs a 829°C eto (athe et anstne (ce enpetre s tiie cond us 1139 4 $m ok coma i 0° 300, and 0 ate mii, The is eae unl temper 300°: Dera etal ps (eRe, ‘Saeed (he cog of oy 11.40 Tho sf ie 32K, 30 KP and auido 9% expan eng Eivioaneucposare Dowrmitctieionsouiprsaresosoh toto 1181 A ow fai, 26 gy a 100K, 350K, an 30 ee bum ene a het ‘cone adie tenth Seam atta ene 0p Tito ks eupeatrc of SH. and anes Mamiya tcp of be et ie PROBLEMS (English Units) S11 A 10.84 ankonnesineagneniatueeat 10 psn and 10°F. The sompositon e040, and 604 CH{,ona massbass [is desred to havea mixture 50% Osan S0%CH cat368 CGMPTER 11 /NONREACTING IDEALGAS ANO GASWAPOR MOKTURES the same temperature and presur. How much mixture most be emoved and how such oxypen added to achieve thi? 911.2 A gus minture hae the following volumetric analysis 208, 30% CO,, 28% He, and 258 CH, Determine a the mass Factions (2) Rast) Ga +113, Two dud seams mix aiahtisly, $000 /mia of CO, $0 psa and 130°Finone stream, and 3000 Rain of CH, a 20 psa an 70°Fin the other. Determine (a) he dnisture temperature), 516 Raq, Afys(@)the entropy production ithe discharge resus 20 psa 14 Referig to Figure 114 let ps abe | tbm ofargon at 100°F and 20 pia and gas bbe ‘iba of helium at 100°F ang 20 pia. The roembrane is removed; find the entropy production ‘118 Referring to Figure 11.4, lt gas. ate $f of sir st 200 psia and 200°F and gas bbe 3 Tbm of bel at 100 pia and [00°F Determine a he final mixture temperature and pressure; (te entropy production, “UL The mola analysis of «gas mixture at SD0°R gad 15 pias 65%, 25% CO,, and 10% 0, Determine a) the mast ration ofeach component; (bits partial pressure, (6) the volume occupied by 20 thm of the mixture *11.7 A gasmisure has components with he folowing mass actions 50%CO,, 20% CO, ane 20% He. Themnsturetemperatureand presuee are :00°F and 20 psi. Determine (a) the moe factions: (6 the paral pressure ofeach component) the mtu pas +118 15 tnk contains |. hep of siuogen and 1.3 thm of carbon dioxie a 77°F Heats transered ntl the tempereure rises wo 280°F. Determine the entropy n= ‘eau of he ae. +119 am aabaie compressor receives 250 bmn ofa gas minture and compresses it {hoon 40"F snd 1.1 pea to 380°Fand73 Spin. The mixtures mass actions are 30% 30% CO, nd 20% O;, Determine (athe power required: (b) the entropy prdue- #110 A minguce of 0.5 pet of nitrogen aed 0.4 pmol of ammonia is compressed isother- tly om 800°R and {4.6 psa to 60 psa, Determine (a) the work required; () the ‘eat transfered) te entropy preuction. HLA Aturbine recived Sbmn/sofa gas mixture at 120 psinand 1000°R andexpandsitto ‘presure of 15 psiaentopicaly The mixture moll analysis is 604 N;, 20% CO,, land 20% water vapor. Determine (athe ent emperstre; (b the poser developed 11.12 Amintorecontainina 30% HeandS0%N, oa amass hasisentersanozlest 30"Fand 15 psa with aveloeity of 150 seo. texpandssentropicaly through the nozzle The «sit veloc from the nozzle i 900 se. Delermine he ext temperature and pes 1443 A gas mixture with a mal analysis of 0% Ny and 40%, enter an adiabatic ‘ompeeso at 1S hans, 1,7 pia, ad 62°F. The discharge pressures 7 psi aad the discharge temperature is 40°F. Determine (a) the second-la efciencs (the wwe (the enttony production 1.14 Two of gas 1 at 600° Rand 13 psa mines adiabatialy wit 68 of gas 2at600°R snd 375 pea, Determine (a the Baal pressure ofthe misture() the enttoy change each ea | | PROALEMS (ngish Unis) 368 1.88 A quantity of neon, 1.2 bm at 68°F and 1 atm, is comtiined in an adiabatic tank Another adiabatic tank contains 1S bm ofntegen at 40°F and § aim. A valve connecting the anksis opened andthe gases achieve equim. Determine each tank's volume; (b) the inal mitre pressure) te ens production. 11.16 The sanks in Problem #1115 ae nonalbstc an the fina miso temperate is 150-F Determine (a the inal pressue(b the heat wansfer, 6 theenropy changeof cach component ‘Two thm of nitrogen at 150°F and 14.7 psa ennes adiabatically with (a) 6 Tom of ‘oxygen, (b) 6 Ibm of nitrogen, both of wbih ae at the same intial condi.ons a the 2 bm of nitrogen. Determine the entropy production, “11.18 An adiabasc unk as two compartments one conning 2 pmol ofearbon oxide at 47°F and 30 psa and the oor containing ? pmol of aitopen2t300°F and TS pia ‘Thegasesmix.and900 Btuof enemy isaddedby aresiance heater, Determine (athe intr final emperatare and pressure: (0 the change in aval) the erevers bly it) = 77°F. 1149 Two bm/se ofhatium sow steadily iso an adicbatic mixing chamser at 180°F ane pia and mix with ntogenentering at S50"Fand 6 psi. The mixture leaves 3s psawitha molalanalysisor508 Heand 30% N,Determine(a the temperature ofthe Intute leaving the chamber: () the at of entopy production "11.20 An industrial process requires a mixture of eittogen and helium at 18 pst, The Instr is created hy adittialy combining} Tonle of nitrogen at 23 sia and TOO"F and (5 Ibm/see of eum at 26 psa and 200"F. The miature leaves the chamber at 22 psia aris thrtled 0 18 pia, Determine (a) the temperature of the ‘mixture exiting the chamber and exiting se thotlng valve; (b) the entropy produc- tion across the camber and aro the erating vale 11.21 The temperature of the ise surface of a rooms eterir wll i 60°F, while the temperatureothesirintheroomis 77°F, What the maxim eave humidity the air te oom can have before condensation oe” Coldwater ows tough pipe inthe basement ofa home ata tempeeature of 83°F “The air inthe basement bse temperature of 12°F. What is the manimaur ative humidity the arean have before condensation occurs? 11.23 A 1004 tank contains atmosphere aie at 80°F with humidity ratio of 0.008 sm ‘apoy/lba aie, What mas of water must beremoved to lower te reinvest a ‘Asoom contains atmospheric ait 7°Fithahwmisity ato of001 thm port Sir What she relative humiity andthe dew point “14.8 Three of air at 14.7 psiaand 80°F with relative humid of $95 re compressed ‘sothermally unl water condenses. At what pressure does the condensation fst *11.26 A mixture of nirogen and water at 148°F and | atm with « moll analysis of &8% nitrogen and 15% water vapor is coved at constant presse At what temperate hoes the water vapor fist condense? “11.27 A pisionslinde wih a pital volume of 0.75 f° contains seat 13°F, 17.6 psi. sn ilrnintvr midi. The sytem ecnolt at tant tal pescae unl teat temperature is 86°F. What are to stem Work ané boat vans”370 CHAPTER 11 / NONREACTING IDEALGAS AND GAS VAPOR MIKTURES “1138 410 tannins intl a 195°, pia 0% eave hay: Hes Shroot Devries chet sere) he ee 138 Ase ankcootsinssira 240, 7p an Oca hums, Tears Sa hetemperstr iF Deere athe alpen es ha ane iShhe sang of nto Reactive Systems 11.0 Ts o/s ofa a 20. 35 p an 3% ete hui expand eo {aly tom evi pete Deerne hele ex presure posible nou cone *1131 A low a tn 26 mesa La, 170°F, nd 34 late huni eee ‘scan ands ied with sore seat ar ith Bote 20 he 9 pres Ia, npertre of Fada ae hoy fa Detrioe $hetemperare ofthe enone mate COMPUTER PROBLEMS CALA The teings trom a sling peycrometer are 90°F dy-bulbtemperatre and 70°F ‘heh emaerature Use PSY.CHRO TK to determine the relative huis C112 Using PSVCHRO.TK, compute the relative hur, huni ato, end enthalpy of| sir With constani well temperature oF 65°F for dy-bulb temperatures between (65°F and 90°F 11.3 Using PSYCHROD.TK, compute the adiaatic saturation temperature ofr ata dy bull temperature of 90°F and 40% esative huis: ‘Very often the frst thought that occurs when the word “combustion” ismentioned is ‘the bueaing or oxidation of hydrocarbon fuels such as gasoline, wood and coal. The ‘change of chemical energy into thermal energy is fundamental 10 mos power producing devices, suc a8 automotive engines and gas turbines. This ehapter will i ‘iscuss hydrocartn fuels primarily: however the fundamentals developed are aso “applicable ro other chemical reactions, such 38 the oxidation of food in lving org nisms, In this chapter you will + Develop a greater understanding of hydrocarbon fuels and their oxidation; + Analyze the combustion process; # Determine the encray released in combustion re * Calculate the maximum temperature acombustion proces can have andlearn ‘of Wass to control the temperature; «Calculate the effets of dissociation on high-temperature combustion: ‘Analyze fel cll fom a hstlaw and secomdlaw view: «Further your understanding of acid rain and global warming370 CHAPTER 11 / NONREACTING IDEALGAS AND GAS VAPOR MIKTURES “1138 410 tannins intl a 195°, pia 0% eave hay: Hes Shroot Devries chet sere) he ee 138 Ase ankcootsinssira 240, 7p an Oca hums, Tears Sa hetemperstr iF Deere athe alpen es ha ane iShhe sang of nto Reactive Systems 11.0 Ts o/s ofa a 20. 35 p an 3% ete hui expand eo {aly tom evi pete Deerne hele ex presure posible nou cone *1131 A low a tn 26 mesa La, 170°F, nd 34 late huni eee ‘scan ands ied with sore seat ar ith Bote 20 he 9 pres Ia, npertre of Fada ae hoy fa Detrioe $hetemperare ofthe enone mate COMPUTER PROBLEMS CALA The teings trom a sling peycrometer are 90°F dy-bulbtemperatre and 70°F ‘heh emaerature Use PSY.CHRO TK to determine the relative huis C112 Using PSVCHRO.TK, compute the relative hur, huni ato, end enthalpy of| sir With constani well temperature oF 65°F for dy-bulb temperatures between (65°F and 90°F 11.3 Using PSYCHROD.TK, compute the adiaatic saturation temperature ofr ata dy bull temperature of 90°F and 40% esative huis: ‘Very often the frst thought that occurs when the word “combustion” ismentioned is ‘the bueaing or oxidation of hydrocarbon fuels such as gasoline, wood and coal. The ‘change of chemical energy into thermal energy is fundamental 10 mos power producing devices, suc a8 automotive engines and gas turbines. This ehapter will i ‘iscuss hydrocartn fuels primarily: however the fundamentals developed are aso “applicable ro other chemical reactions, such 38 the oxidation of food in lving org nisms, In this chapter you will + Develop a greater understanding of hydrocarbon fuels and their oxidation; + Analyze the combustion process; # Determine the encray released in combustion re * Calculate the maximum temperature acombustion proces can have andlearn ‘of Wass to control the temperature; «Calculate the effets of dissociation on high-temperature combustion: ‘Analyze fel cll fom a hstlaw and secomdlaw view: «Further your understanding of acid rain and global warming372 cuapren 12 /nencrive systEns 42.1 HYDROCARBON FUELS ‘One ofthe basi constituents in the combustion reaction is the fuel we willbe dealing ‘with hydrocarbon fuels —soid, qui, or vapor. The most important form of solid hdracasbon iscoa, hich is minedin several grades, ranging from anthracite (hard) tobituminous (sof), Coal is misture of carbon, hydeogen, oxygen, nitrogen. sulfur, ‘water, and a noncombustible solid material ash hn quid iydrocarbons, suchas gasoline, kerosene, ancl fuel oil, are obtzined by thedistilation of peteolewm, Theieadvantages over solid fue! are cleanness and ease bt handling and storage. The chemical farm ofthe liquid hydrocarbonsis C,H, the ‘values of subscripts x and )'depending an the hydocatbon family. Any fuel, such as asoline,isactually a mixture of many hydrocarbons. Except in sophisticated anal Sn the predominant hydrocarbon is assumed to be the only one present, oF an fverage of the several constituent hydrocarbons is taken. Alcohols are sometimes tse a fel in internal-combustion engines In alcohol one ofthe hydrogen atoms in the hydrocarbon is replaced by the OH radical. The resulting hydrocarbon is @ Carbohydrate and is written CyH,OH. In this txt, unless specifically noted, we will consider gasoline 1 bea single hydrocarbon, CyH (octane), and diesel fuel tobe a Single hycracasbon, C,H, (dodecane) ‘Gaseous hydrocarton fuels also are a mistuce of various constituent hydrocar bons. They have nearly complete combustion and are very clean, The products of their combustion do not have slfur components, hich have adverseenvironmental tffecs. There are great diferences between natural gos, hydrocarbon fue! found Underground, and manufactured gas, These differences lie inthe proportion of the ‘onstituents found in each, as Mlusrated in Table 12.1 12.2 COMBUSTION PROCESS The combustion process isthe oxidation ofthe uel constituents, and we may writean equation describing the reaction, During the combustion process the total mass femains the same, s0 in balancing reaction equations we are applying the law of | Conservation of mass, Actually there isa slight reduction in mass from Finstin’s fquation £ = mit, but his sextcomely small, on the order of 10-! g/kg fel, and fan be neglected. {TAOLE 12.1. VOMUMETR ANALYSIS OF SOME FLELGAS MOXTURES (NUMBERS ARE PERCENTAGES) Om Ge GO Coal ax » pe Preducereas 29 2% 08 - — 4 2 Basfunaeeas 27 2 = — = = th oO ‘atu! ga Pf os 3 DOD 4 tat eee ee te oe ee re cera pee eee one) ees bee 0) 22 COMBUSTION PROCESS 373, ‘We will frst consider the complete oxidation of carbon and, in so doing, define the terms commonly used in combustion-reaction analysis Reacsanis Pr +000, (24) In this action, carbon and oxygen are the initial substances, that is, the reactams They under chemi renton, ling erton dosh fa susan product. Furthermore, we see that 1 mol C+ 1 mol +1 mo! CO and since there are 12 ka/kgmol for carbon, 32 kg/kamol for oxygen, and 44 kg kgmol for carbon dioxide, I2kg C+ 32 kg O, +44 xg CO, Similar, the hyiragen in the fuel reacts with oxygen to fost water H, +05 0,10 | mol H;+0.5 mol O,—> | mol H,0 2 kg Hi, +16 kg O,—> 18 ke HO. When a hydrocarbon fuel is completely oxidized, the resulting products are primarily earhon dioxide and water, Le us consider methane as the fie CH, + 20, > CO, + 2H (22) The water may exist as a solid (5), liquid (), ot vapor (v), depending on the final product temperature and pressure, This isan important consideration when we perform energy balances later in the chapter. In the oxidation process, many Feac- tions oacur before the final products in equation (12.2) are formed. These interme siate reactions constitute an important area of investigation, but we will be com cerned with anly the initial and final products Combustion with Air Most combustion processes depend on ait, not pure oxygen. Air contains many consiuents,particuleely oxygen, nitrogen, argon, and other vapors and inet gases, Its volumetis, or mola, composition is approximately 21% oxygen, 78% nitrogen, and I") argon. Since neither nitrogen nor argon enters into the chemical reaction, we will assume thatthe volumetric ai propartions ae 21" oxygen and 79% nitrogen, snd that for 100 mol of ai, there are 21 mol of exygen and 79 mol of nitrogen, of FP 376 mot N,/mol O: To account for the argon, which we include as nitrogen, we use 28.16 a the equiv lent molecular weight of nitrogen. This isthe molecular weight of what is called ‘mespheric nitrogen. Pure nitrogen has molecular weight of 2.016. In analysesin ‘which great accuracy is desire, this distinction should he made. However, we will consider the nitrogen inthe arto be pure.374 CHAPTER 12 /REACTVE SysrEMS 12.3 THEORETICAL AIR ‘The combustion of methane i ar is cH 10, + 23.76) +00, #2H,0+7, Ns 023) “The nitrogen does not enter into the reaction, but it must be accounted for. There is 3.16 mol nitrogen per mole af oxygen, and since 2 mol of oxygen is necessary for the oxidation of methane, (243.76) mol oF nitrogea ispresent. equation 12 3)only ‘he minimum amount ofoxygen necessary to complete the reaction is incladed in the ‘equation, The minimum amount of air required to oxidize the reactants is the theoretical ar. Waen combustion sachieved with theoretical as, oxygen isfound inthe produets. In practice, this is not possible. Additional oxygen is required to achieve complete combustion ofthe reactants. The ewess airs needed because the Fuels of nite size, and each droplet must he suirouded by more than the necessary ‘number of oxyuen molecules to assure oxidation of all the hydrocarbon molecules. ‘Thisexcess iris usually expressed asa percentage ofthe theoretical ae. Thus, 25% ‘more air than is theoretically required is used, this is expressed as 125% theoret eal ait, or 25% excess air. There is 1.25 times as much eit actuelly supplied than is theoretically required. The combustion of methane in 125% theoretical ait is thus CH + (1.2510}05 + (.25)2K3.70)N5 > CO, +2H,0+94N, +050, (124) Equation (12.4) is balanced by fist balancing the oxidation equation for theoretical sirand then multiplying the theoretical air by 1.25 io account fo the 125% theoreti- ‘al ir and adding 2 term to the products for the excess oxygen. The amount of| nitsagen and oxygen appearing in the products is determined by a mass balance on ‘each ler lite excessairisinsufcient to provide complete combustion, natallthecarbon ‘willbe oxidized to carbon dioxide; some wil he oxidized to carbon monoxide, When there is considerably less theoretical air, unburned hydrocacbons wil be present in the products. This is the soot or black smoke that sometimes pours from chimneys and smokestacks when one or more of the following three conditions for complete ‘combustion have not been met 1. The sire] misture must be atthe ignition temperate 2. There must be stficient oxygen to assure complete combustion 3. The oxygen must be in intimate contact withthe fuel Smoky products of combustion during start-up operations usually result From a failure to satis requirements | and 3, To balance the combustion equation when incomplete combustion accurs, we need information about the products. For ine stance, assume tha, with theoretical ai, the oxidation of carbon i 90% complete in : 4 124 Ai/fues NATO 375 the combustion of methane: then CH, + 20, + 20,70, 0900, +0.1C0 + 2H,0+72N,+0050, 025) 12.4 AIR/FUEL RATIO ‘Two important termsin the combustion process give us the proportion of at fuel these ae the arf! ratio, Fay, and it reciprocal, the fuel/air rari, rp. Bath mas be expressed in tems of the moles or the mass ofthe fel and ir present Example 12.1 | A fueloilis burned with 50% excessair, ancl the combustion characteritiesofthe fue oil are similar to C,H. Determine the air/fuel ratio ona massand mole basis and ‘the volumetri (moll) analysis ofthe products of combustion. Solu Give {A specified fuel oil and the exces air to oxidize i¢ completely Find: ‘The sirTuel ratios and the volumetsc product analiss. Assumptions: 1. The combustion of the Fuel is complete; no CO is formed 2. The molal ratio of nitrogen to oxygen i 3.7 4. The products behave like an ideal gs. analysis: Fist she reaction equation must be balanced for 50% excess air, oF 150% ‘theoretical ic. Apply the conservation of mass to each reactant for 100% theoretical Cas + oO, + 3.75aN; = 1C Chatance 12=b H, balance 26= 2c +aN; cB 2465=185 9.56 Os balance a= b+ e2= Nabalance 3.760= d= (3.76)18.8) This balances the equation for 100% theoretical ae. Now mulhiplytheairserms ofthe reactams by 1.5 and add an excess oxygen term fo the products, The allowing ‘equation results CiHgg +27.780, + 108.34N,— 1200, + 13H,0 + 104.34N, + 9.250,376 CHAPTER 12 /REACTWE SYSTEMS ‘The rfl ratio on the mole bass is found by dividing the moles of air bythe moles of Fue in the reaction equation. _ (2175 + 104,34 mol air) 1g ally 132.1 mol air/mol fuel ‘The ratio on the mass basis is found by multiplying the moles by their appropriate ‘molecular weight, The molecular weight for C,,Eemay befoundin Appendix Table Cu (132.1 mol 2i9(28.97 kg/kgmol sie) (F mol Fue(170.328 kgm Fuel) In determining the volumetric analysis ofthe products, fnd firs the total aum- ber of moles of product and then each component's faction of the total The total moles of product is 12+ 13-4 104,344 9.25 = 138.59 mol = 22.46 ka aif fel “The molal analysis then co, 0. 2/138,59 = 0.0866 3/138.59 = 0.0938 104,34/138,59 = 0.7529 25/138.59 = 0.0667 Comments Wien balancing equations with excess ar, tart with the LOO4 theoreti cal air equation and modify it fr exces air. = Example 12.2 Determine the dew point of the products at 1 atm for the liquid fuel oxidized in Example 12.1 ifthe air supplied is dry at 28°C, and ithe ar supplied is at 28°C with 50M relative humidity. Solution Given: ‘The balanced reaction fora hydrocarbon ful and its total pressure and the reactant air condition Find: The dew point of the product Assumptions The products behave lke an ideal gas, 2. The molal ratio of nitrogen to oxygen is 3.76 Analysis; The Balanced reaction equation from Example 12.1 is CyHys + 27-750, + 10434N, + 12CO, + 13H,O + 104.34N, + 9.250, 12a amyrua sano 377 ‘The mole fraction of wate in the products is 0.0938, From Dalton’s law of partial pressures, the vapor pressure of water contributing to the total pressure is (0.0938X101.3 kPa) = 9.5 KPa “The saturation temperature corresponding to this pressure is 45°C, which is als the ‘dew point temperature of the products when dry air is used in the combustion process. ‘When atmospheric airs used with water vapor present, the reactants ide carries water vapor term, which sadditive to the water vapor formed from the combustion reaction. First we need tofind the water vapor presentin airat 28°C with Sfbrelative ‘humidity. Using the terminology of Chapter 11,2, 3.8194 kPa and the vapor pressure of wate, 7,15 (0.5)3.8194) = 1.9097 kPa. The rest of the reactant pressure is supplied by the air. The liquid fuel does not contribute to the total pressure. Thus, pis Po= 1013 = 19 = 99.4 KPa “The humidity ratio is (0.622K1.9) 0.0118 kg vapor ke air Pe Tis needs to he converted to an equivalent value on the mole bass, @” = 0.019 mol vanos/mol a 1m this problem 132.1 mol of air oxidizes 1 mol of fuel, so yo = (0-019 mol vapor/mmol aitX(132.1 mol air)» 2.51 mol vapor “This is additive tothe total moles of vaporin the product and to the total number of moles of gasin the product. Thus, there ae 15.51 molof water vaporin 141.1 mol of product. The purl pressure ofthe water vapor is 101.3Y05.51/141-1)= 11) kPa “The saturation temperature or dew point, associated with this pressure is 48°C. Comments 1. Most often dry air i used in reaction equations. The gain in aceuray of using ‘moist ar soft by the increased complexity of the calculations 2. The dew points often sought in combustion reactions because when the temper ature of the products falls below this value, water precipitates, Should precipits tion occur, the liquid water wil contain dissolved gases, forming a corrosive substance. To prevent this, the temperature ofthe products of combustion iskept well above the dew point in smokestacks and exhaust piping 3, Insteam generators burning fuel oll, atomizingsteam i often used toatomize fue] droplets. typical value i 0.03~0.08 kg steam fuel, A similar analyse woul bbe made to find the moles of water used and their effect in raising the dew point of the produc. =378 CHARTER 12,/REACIVE SusTEMS ‘Coal has played an important roleasan energy sourcein the past and will become increasingly important as oil and natural gas become more expensive. Coal has & variable chemical composition, since it originally was vegetation. Its essentially & hydrocarbon fuel, with impurities such asentrapped water and ash that represent he inorganie matter that does not oxidize. The ultimate analysis of coal includes ll the ‘constituent mass fractions, The prositnate analysis alo ona mass asi, soften used to define the percentage of carbon in the coal that is % C= 100% — 4 ash ~ 9% moisture ~ 4 volatiles “The volatiles are those compounds that evaporate at a low temperature when coal is heated. The following example illustrates these concepts Example 12.3 An ultimate analysis of coal yields the following composition: 74% C, 3% H., 6% O;, 116, 1.2% Nz, 38% HO, and 9% ash. Determine the theoretical 3e/fuel ratio. Solution Given: Ultimate analysis of coal. Find: Theoretical air/fuel ratio, Assumption 1. The molat ratio of nitrogen to oxygen is 3.76 2, The products behave lke an ideal g28. Analysis: Since ash does not enter int the oxidation of coal, determine the mole fractions ofthe coals constituents on an ashlesshasis. First divide the mas fractions by 0.91, then divide by the molecular mass. Finally, divide by the total moles to determine the mole fraction, xm © 0813 120 007 agra H, 005520 O42? Ome ©; 0066 320 0.02 GoaL Sool 320 00m oon Ni 0013 280 0.0008 ons Ho 00:2 iko gous ams 1-000 00 L000 14 amsrust Rano 379 “The combustion equation for | mol of ashless fuel is a et 0.674C + 0.2741, + 0.0210; + 0.0035 + 0.00SN, + 0.02311 — Air 4 gO, + BN, + CO, + dH,0+ #50,+/N; Perform « mats balance on each term ofthe reactants, Chalance ©= 0678 Hy balance 2d 2(0.274 + 0.023) Sbalance ¢= 0.003 ©, balance 0,021 + 0.0115 +a= 0.674 + 0.148 + 0.003 Nz balance (0.005) + (3.76)0.792) =f f= 2.985, ‘The air/fuel ratio on the mole basis is = (4:26}0.792) mol air fag ol fuel) ‘The air/fuel rato on the mass basis equines that we determine the molecular weight of the fuel. This mast be found on an ashless basis, the one represented in the ‘combustion reaction, from M= 3. y,M,. Thus, = 3.77 kgmol aie/kpmol fuel Meu ~ (0.674912) + (0274)2.016) + (0.021)(32.0) + (0.003332) + (0.005)28.016) + (0023) 18.016) Muu = 9.96 kaykgrnol (6.77 kgm ait(28.97 kg/kemo ai) Cred FueiX9.96 krkemo! fae) ‘7ag™ 10.96 kg air’ fet Comment: The fuel must be represented by an ashless percentage to correctly balance the reaction equation. = Acid Rain and the Greenhouse Effect Residual fuel and coal often have constituents like sulfur that when bucned cause problems, Sulur forms sulfur dioxide and sulfur trioxide inthe combustion process, tvhich awhen combined with water form sulfuric acid, This is one of the primary ‘constituents of acid rin, ass nitric oxide, formed in high-temperature combustion processes involving air. Phe high temperature causes diatomic nitrogen to dissociate into monatomic nitrogen, which is cheracally active and combines with oxygen to form nitric oxide. When nitric oxide dissolves in water, nitric acid is formed,320 ‘The carbon dioxide formed in the combustion proces is increasing the ereen- house effet of the earth's atmosphere and accelerating the warming of the earth, Caron dioxide concentrations in the atmosphere are 25% higher than preindustrial levels. Carbon dioxide is not alone in cresting the greenhouse effect, but itis 2 primary contributor. The average global temperatures are O.6°C higher than 100 years ago, and they are rising. Computer models predict an average temperature increae of between 2.$ and 4.8°C by the end ofthe next century. These temperate rises wil change the world climate, Growing seasons in the Northern Hemisphere ‘ray increase by several weeks, but thisis offset by drought conditions in many of the ‘curently temperate repions. Melting of polar ice caps will cause sea levels to rise, Aooding coastal areas “Te greenhouse eifect is the reason the tempersiure ofan automotile's interior with the windows closed is warmer than the outside air on a sunny day, When its ‘wavelength s shor, sunlight passes through glass, which i viewed a being iranspar ent tothe radiation. The sun's radiation hits 2 surface inside the ar, isabsorbed, and is ceradiatd, The wavelength ofthe ceradation is Longer, and the glass is not trans- patent fo this radiation, but opaque and traps the enerpy within the ears interior ‘This is also how a garden greenhouse works, Certain pases, catbon dioxide for in- stance, at lke lassi sola radiation, forming a “greenhouse” around the earth, ‘We can calelate the magnitude of these terms quite easily. The gravimetric analysis athe fue tells us the percentage ofthe various constituents in each nit mass of ful. For instance, ful oil may contain carbon, hyéeogen, sulfur, water, and as, Let's say thatthe fuel contains 1% sulfur and 904 carbon and thatthe cleaning processes om the sack remove 98% of the sulfur dioxide ram the combustion ges, Calculate the kilograms of sulfur and carbon dioxide that are released daly om a ‘power plant that burs 3 000 000 hg of fel dail Tally let us determine the total mass of sulfur that willbe emitted From the stack The dally mass of fuel burned is i= 3.000 000 kayday rig (0.0113 000 000) = 30000 kgiday How2ver, 98% ofthis i contained, s0 only 2% ofthis value leaves the stack. Pens = 600 helday The sulfur reacts wth oxygen to produce sulfur dioxide according to the Fllow= ing eaction equation S +0; +80; 32 kg S+32 ka 0, = 64 ke SO, “Thus, for every 32 kg of sulfur oxidized (burned), 64 kg of sulfur dioxide is formed. L's just consider the sulfur that escapes 4 ky SOs ae af SP! * 600 ke S/ay = 1200 kg SO, released day This amounts to [.32 tons per day from this one plant, Imagine the amount that could be released if scrubbers were not installed, Not al industries nor all countries use exhaust gas serubbers. po i 125 PRCOUCTS OF COMBUSTION 361 “The tons of carbon dioxide produced may be found ina similar fashion. ‘Me™ (0.93 000 000) = 2 700 000 ke/day C+0, +00, “Thus, there are 44/12 = 3.667 kg of carbon dioxide produced fo eat ilogearn of carbon completely oxidized co, ~ (3.657 kg CO, /ke CK2 700 000 kx C) = 9900 000 ks CO. day £890 tons per day— from one power plant This is equal to 1 DUCTS OF COMBUSTION Inpowerplantsand other facilities using lage amounts offuel.itisimportant thatthe ‘burning be as eficent as possible. Tiny incteases in efficiency (even a faction of (%) can save thousands of dollars. One important factor affecting the efficiency isthe amount of excess air. not enough ai is used, combustion willbe incomplete, and ‘ot all the chemical energy of the fuel will be used. 100 much ar is used, the heat {eleased by combustion is wasted in heating this excessar. The abjectisto oxidize the fuel completely withthe smallest amount of ait. Tis wil yield the greatest release of energy per mass of air. How may this be determined? Orsat Analysis An analysis of the products of combustion tells us how much of each produet was formed, The Ort apparatus performs thistask by measuringeatban dioxide, carbon ‘monoxide, and oxygen volumetrically. Thecombustion gasispassed through various chemicals, which absorb carbon dioxide, carbon monoxide, and oxysen. The vol imetric decrease of the combustion gas is noted at each ste, and the decrease in volume divided by the intial volume gives the percentage ofeach combustion prod: uct. The remaining volume isassumed tobe nitfogen. The Orsatgvesthe volumetric proportions on a dry basis; the amount of water vapor cannot be determined, since it ‘condensed as igui inthe sampling and measuring processes. Since the analysis ‘usually occurs at room temperature and pressure, which is below the dew point of ‘most hydrocarbon products of combustion, the error involved is quite stall. “The Ors analysiscannot measure partially combusted hydrocarbons, noreanit, smeasurecarbon, These quantitiesare important in dealing with intersal-combustion egies, where the combustion is not complete and we want to analyze reactions Docuring before the final products are formed. There also may be nitric oxides formed at high temperatures. Measuring devices, such as gas chromatographs can determine these compounds, bur these problems are beyond the scope of this book ‘They involve reaction times and partial reactions: we will consider only coutplete combustion and no time-dependent reactions at all. "The traditional Orsat apparatus can take only periodic measurements In order {a provide powerplant operators with continuovs information about tie combustion302 process, various electronic instruments have been developed. The most popular of these ate ditec-inserton (in situ) oxygen analyzers using a zirconium oxide (Z/O.) sensor cell. The sensor cel i installed dineetly in the stack gas flow. The gases of ‘combustion pass across one side ofthe cel, an the other sie is exposed to atmes- Dheric air. A heater assembly maintains the cll at a constant temperature of about 815°C. At chis temperature, oxygen ions passthrough the ZrO; ell generating 2 ‘voltage proportional to the logarithm ofthe ratio af the oxygen partisl pressures, 10 ‘many modern boiler installations, the output ftom the analyzers used by the com- ‘bustin control system to automatically regulate the eel ratio “The principles wed in an Orsat analysis will be demonstcated in the examples, \We ean determine the air/fuel ratio as well as balance the reaction equation Example 12.2 Fueloil, C,H, is burned in air at atmospheric pressure, The Orsatunalysis forthe prodvets of combustion silds 13.1% COs, 2.0% O;, 0.2% CO, and 4.7% N, Determine the mass air/fuel ato, the percentage of theoretical air. and the combus- tion equation, Solution Given: The Orsat analysis ofthe products of known fe. Find: The roas ar/tve! ratio, the percentage of theoretical air, ané the balanced combustion equation. Assumptions: 1. The products behave individually and collectively ike an ial gas 2, The molal ratio of nitrogen to oxygen in ae is 3.76, Analysis: Wrivethecombustion equation for 100 molofdry products, asthisallows "so write the percentages asthe numberof moles, The unknown coeiciens onthe reactant sie ofthe combustian equation may be deterined by applying the conser- ‘ation of mass to each reactant. aC Hy, + HO, + eN, + 13.100, + 0.260 + 2.00, + 847N, + al Chalance 120 31402 a Ngbalance ¢= 84,7 N,/Os ratio § Hira ate (28)e) dea Divide the equation by ato determine the combustion equation for 1 mol ful, Calls, + 20.30 + 76.41N,—* L1.ACO, + 0.18CO + 1.80, + 164N; + 13H,0 125 PRODUCTS OF COMGLSTION 359 “The air/fuel rato is jo 203-4 164 mol ai92897 bgtkgm) 0 Ho eh 170-328 kako 16.45 ke ain fuel The balanced revetion equation for 100% theoretice! ai is Cutins + 860, + 18.5(3.70N;— 12CO, + 13H, + 69.56N, sand the airtel ratio is 18.5 + 69.56 mol ain(28.97 ka/kemal as Tol Tue 170.328 kearkgmol) 14.98 ke air fuel “The percentage of theoretical aris 45 oretical air HSE 1.8% “Theoretical aie HESS x 19) = 109.8 Comment: 1: is crucial to include water on the products side ofthe combustion fsquation, a the Orsat and other analyses do not account for this. = fj Gxample 12.5 © An unknown hydrocarbon fue, burned in ais, hasthe following Orsat analysis: (C0, 0.345 CO, 3.1% O,, and 84,144 Nz, Determine the mass ait fuel ratio, the fuel ‘composition on a mass basis, and the percentage of theoretical ait. Solution Given: ‘The Orsat analysis ofan unknown fuel burned in an ‘ofthe fue, the mass seul ratio, and the pereentage Find: The masscompos of theoretical air Assumptions: 1, The products behave individually and collectively lke anid 2 The mola ratio of nitzogen to oxygen in air is 3.76 Analysis: Write the reaction equation for 100 mol of dry products and perform = mass balance for each of the unknown quantities. CyHly +c, + dN, “+ 12.500, + 0.300 + 3.103 + 84.1Ny + €H,0 Chance a= 125403128 N, balance 7 = 22.36 Opbolance 2236=125+ 98 +3144 em 132 2 3 Hybalance b= 2e~ 264ae CcuamteR 12 /aeAcrVE SYSTEMS ‘The balanced reaction equation is CyagHlaga 4 22.380, 4 84.1,» 12.5CO, +0.3C0 + 3.10, + 84.1N, + 13.2H,0 ‘The molecular weight ofthe fuel is My~ (1201 kero! C)(12.8 mol C) + (1.008 ka/kgrmol HX26.4 mol 11) M,= 180.34 ka/kamnol ‘The air/fuel ratio on a mass bass is (22.36 + 84.1 mol ain(28.97 kg/kgmol) _ (mol fuel 180.34 Ke/kemol) 17.1 kg arg el ton equation balanced for 100% theartial air is CaesHacs +1940, 473 and the ai/fuel ratio is (19.473 mol ain(28.97 karkemol) (E mol fuel 180.34 Kgykgmol) eens “The percentage of theoretical aris 4 ox tt ‘The fuel compesition on a mass basis is 12.8 mol Cy(12.01 kg/kgmol) T mol fuel\ 180.34 ke/kemo)) {26.4 mot HY(,008 kg/kemo!} T mot felX 180.34 kg/kgmol) Comment: tis not necessary 10 know the fuel type t0 establish the combustion ‘uation. The products of combustion would indicat the other combustible mater. als in the Foe! but would not indieate compounds such as water, nitrogen, andl ash 852 oF 85.2% = 0.148 or 14.8% ‘The TK Solver model ORSAT.TK ean be used 10 analyze the products of a combustion process. The back-solving capabilities of TK Solver permit the same ‘model to determine the tack gus analysis, given the fuel analysis and excessair,orthe fet composition and excess ar, given the Orst stack gas analysis Example 12.6 Repeat Example 12.5 using ORSAT.TK. 125 PRODUCTS OF COMELSTION 305 Solution Given: “The Orsat analysis of an unknown fel burned ina. ind: The mass composition ofthe ful, the massairfuel ratio, and the percentage of excess ar. Assumptions: 1. The products behave individually snd collectively ike an ideal eas 2. The mola ratio of nitrogen to oxygen in air is 3.76 Jaan he Vase nays oa ORSAT-TE i TK. Sone an inputted ino de Vardi Seabed nine tesa mgr omen sna comentt Tesh sed Vane ets Comment: ORSAT.TK permis convenient anasisaf the producs ofa combus, tion proces.386 ENTHALPY OF FORMATION Inthe previous chapters the working substance has always been homogeneous and never changed its chemical composition during any proces, Tables were developed sleseribing the properties ofthese substances —for example, the seam lables —and in these tables there was always an arbitrary relerence hase, Theenthalpy of saturated Tiguid water at Cis zero, Ths is an arbitrary base, butt des not matter since we {eal with changes in the enchalpy as with changesin any'other property. In chemical reactions. however, lhe substance inthe system changes during the course of the process, so the capricious use of arbitrary standards foreach substance woud make the energy analysis of the process impossible, ‘To overcome this dificult, the enthalpy of al elements is assumed to be zero at an arbitrary reference state of 25°C (77°F) and 1 atm pressure. The enthalpy of formation of compound ists enthalpy at ths temperature and pressure, Consider steady-state combustion process inwhict | mol ofcarbon and L mol of oxygen ac the reference state af 25°C and | alm pressure eombine to produce 1 mol of carbon dioxide. eat is transferred, so the carhon dioxide finallvexissat the reference sate. Figure 12.1 demonstrates this process ‘The reaction equation is C+0,00, Let Hy be the total enthalpy ofall the reactants and Hy be the otal enthalpy ofall the produlets per mole of fuel, The frst la for this proces is Ot Hy= Hy (26) ‘where the surnmations are overall the reactants and al the produets, and Q= Gite ‘Since the enthalpy af all he reactants s zero (they are al elements). We find that Ont where the heat transferred has heon carefully. measured and found to be 393 757 KJ, The sign is negative because heat is lowing from the comtta volume, ‘opposite to the assigned direction in equation (12.6) The enthalpy of carbon dioxide atthe roference state, 25°C and | atm pressure, i the enthalpy of fvmation and is 93.087 hI 028) Fowe 121 4 seadytat combustion po- ces heat raster * 127 ERSTLAW ANALYSE FOR STEADYSTATE REACTING SYSTEMS 387, Figure 122 A sicadsfow system where a L heme easton transfor hes and pro designated by the symbol i. Therefore, (ijheo,=~393 757 kage (29) Tine negative sign for the enthalpy of formation islue to the esetion’s being exo ic; heat i released from the combustion of carbon and oxygen. Since the energy rtust be conserved inthe reaction and 393 757 J let he control volume, the enerey Of the carbon dioxide must be fess than the energy of the reactanis by un amount ‘equal othe heat transferred, The enthalpy ofthe reactants is zero 25°C and | ati therefore the enthalpy of carbon dioxide at 25°C and 1 atm must be negative “Table C. lists the enthalpies of formation for several substances 42.7 FIRST-LAW ANALYSIS FOR STEADY-STATE REACTING SYSTEMS In general he steady-state combustion process wll ans heat ad prluce work a illustrated in Figure (2.2. An energy balance would vield OFS nie +S nh, (210) where H°= Hii, The enthalpies of formation may be readily used in this analysis, since they areal relative tothe same reference base. Usually the analysis is done per ‘mole of Fuel, thus the unitsarekilojoules perkilogram-mole. The following examples illustrate important concepts that may be used in combustion energy araiyss Example 12.7 Propane, CsHy, undergoes a steady-state, steady-flow reation with atmospheti it Determine the heat transfer per mole of fuel entering the combustion chamber. The reactants and produets are at 25°C and | atm pressure Solution Givene A known fuel completely oxidizing in a combustion chamber at a steady state‘ouapren 12 nencTVe ystEns Find: The heat sransfer per mole of fel ‘Sketch and Given Data Ea, Figure 12.2 sumptions 1 The water in he rot aight temperatures low he ew point 2. The motal ratio of nitrogen to oxygen in air is 3.76. = 5 Noworkie don 4. Thecange fn inti and poe energies may be neglected Analysis: The balanced reaction equation for 100% theoretical aie is CyHy + 50, + 53.76)N;— 3CO, + 4H,O11) + 18.8N, The firs-law equation with assumprions 3 and $ invoked yields Or Rahim BHA, Since the enthalpy ofall the clementsat25*Cand | atm iszero thesumimation terms contain only the enthalpies of formation for the compounds, which are four in Table C.1 BS aF= ease =~ 103 909 Kiker! Bh = Mipeo, + 47 no = -2 325311 Wig} = =2221 402 43/kpmol fuel Comments In most cases, neither the reactants nor the product are tthe reference condition of 25°C and t atm pressure. In these cases we must account forthe property change betveen the reference ate and the actual state, Table €.2 tabulates {te change in enthalpy betwen the reference state and theactualstte. f° ~ fq) in Aulojoles per Kilogramemoles, The temperature ofthe reference stein absohate notation i 296°K. The superscript" denotes that the pressure is 1 etm. I these tabulate values are not available, We have fo use the ideale law, i= G7, deter ‘ining the pectic heatby the best means available, For example, ithe spceife at 127 FRSTLAW ANALYSIS FOR STEADYSTATE HEACTING SYSTEMS 389) varied asa function of temperature and this functional relationship were known, this ‘would be used. If tables of property values existed, such asthe gas tales or steam. tables, then these, too, could be used. ‘Most problemsin thistextareat | atm pressure. Thsis thestandard pressureand the one found in mast combustion reactions, When ic is necesaty 10 include the pressure effects, as when calculating entropy changes. the reactants and produets must be expanded tothe reference state and the change in doing so included in the Calculation. This sa very smal effect and need not be included in most engineering applications. Tn general, the firs aw fora steady-state, steady-Now reaction may be O+ 3 ally +0" —ligak— s+ SD afhy +0 — Few), 02.20) ‘where changes in kinetic and potential energies are considered neuliible. This will always be assumed for problems i this text Example 12.8 A igsel engine wes doecane, CoH) for fuel. The fuel andairentertheeagineat 5°, The products of combustion leave at 60°K, and 200% theoretical aris used ‘The heat loss from the engine is measured 232 000 kI/kgmol fuel. Determine the work fora fel How rate of | gmol/. Solution Given: A diese engine receives fuel and airat 25°C and a known ratio offusl tat Complete combustion occu, with the products temperature known as well 35 the heat transfer from the engine Find: The power fora known fuel Bow rate Shetch and Given Date Aiwec Prats 60° Powe 1204 Assumptions 1, The products behave like ideal eases 2, The molal ratio of nitrogen to oxygen in aic is 3.76. 3. The changes in kinetic anc potential enemies may be neglected390° CHAPTER 12,/AEACTVE SySTEMS Anolysis: “The balanced reaction equation for 200% theoretical air is CuByle) + 2118.5)0, + 118.513. 79N,~ 12C0: + 13H,0-+ 18.50, + 139.12, Apo the fcst law per mole of fact +3 nll +06 -Fi Hol, = WY nfp+ OP ~ his, “The hea transfer per me of felis Q=—232 000 k/kumol us. The reactant and product energy terms may now be evaluated: Dds +0 — Rah = Wich = =290 971 kaykemo! 3) = 11-393 757 + 12 9160, + 1N=241 971+ 10-498)n9 +139.12(8891)y, + 18.519247)p, 6 171 255 ki/kemal fuel, Substitute these terms into the Brstlaw equation OF Hg= Wt Hp 232 000 ki/kgmal fuel ~ 290 971 ki/kemol fel = 6171 255 Ki/kgmol fuel rm § 688 284 U/kg fuel Maliply the work per mole of fuel by the fuel ow rate (1 kamo/aNS 648 284 1 /kgm (Gé00 sihy waa = 15089 kW Comment: The frst law is usually solved per unit mole of fuel, asthe reaction equation is balanced for 1 mol of fuel, The rate of energy change is calculated by ‘multiplying the energy change per mole by the molar fe flow rate ms Example 12.9 A gas turbine generating unit produces 600 kW and uses CyH y() fuel at 77°F; 400% theoretical air is use, and the air enters the unit at 100°F. The products of Sonbosion sweat 00°F The ea wunertthesurounngas0Gue ake Determine the fuel low rate in pounds mass per hour for complete combustion, 4 ‘Solution || Given: A gas turbine unit with known fuel and air temperatures entering and a products’ temperature leaving. In addition the heat transfer and the power produced 2 Teele 1 127 FRSTAAW ANALYSS FOR STEADYSTATE REACTING SYSTEMS 391 Find: The fue! Bow rte Sketch and Given Data: aE ll Le reno ! fe st sone sao 800 Fowe 125 Assumptions: 1. The products behave like ideal gases 2. The molal ratio of nitrogen to oxygen in ar is 3.7. 5. The changes in kinetic and potential enexpies may be neglected Analysis: ‘he balance teation equation for 400% dheorstial ses Cll) + (12.590, + 4(12.5\3.T6)N; > 8CO, = 9H,O + 37505 + ISBN: Determine the values of Hg and H forthe | mol of fuel oxidized in the combustion equation Hg Sy +O — Rigph-= = 107,532} + $0165, + 18862 Hg =~ 68,826 Btu/pmol fuel fly + 0° — By (~ 169,297 + T6810, + (104.036 + 6102}40 4 ITS(S378p, + 18815139)y, 1,007,599 Bru/pmot fuel Hy Hy ~ Hy = ~938,773 Buu/pmol fuel “The ist aw is Oo nyttg Willy OH Wa ily He) 600 KW = 2,047,680 Bru/hras ‘conpren 12 / REACTIVE STEN Substituting into the frs-law equation, $0,000 Btu/he ~ 2,047,680 Btu/hr~ f,(—938,773 Bto/pmel fuel) y= 2.235 pmot/he ‘The molecular weigh ofthe fuel is 114.23 on/pmok; hence the mass flow rate is ri (2.235 pmol/nr\114.23 Ibm/pmel) 85.3 Ibe Comment: Care ust be exercised that all units inthe ist-law equation are the same, Do not mix tems that have units of energy per mole of fuel with hose that have energy per unit time, fa Example 12.10 ‘A mixture of methane and oxygen, in the proper ratio for complete combustion and at 25°C and 1 atm, reacts ina constant-volume calorimeter bomb. Heat is trans. ferred uni the products of combustion are at 40°K. Determine te heat transfer per mole of methane and the final pressure Solution Giren: Known resctans oxidize in aconstant-volume container. The products are ‘cooled to 400°K Find: The heat wansferred per mole of fuel and the final pressure Sketch ond Given Data: VEEN af roduasot S| ote sate sue? Figure 126 Assumptions 1. The reactants and products behave lke ideal gases. 2. The water im the products isa vapor. 3. Na work is cone 44 The changes in kinetic and potential energies may he noglected Analysis: The combustion equation is CH, +20, + C0, +240 12.7 FRSTLAW ANALYSS FOR STEADYSTATE REACTING SYSTEMS 35 “The firs-law equation for constant volume, invoking assumptions 3 and 4.18 On Us UT yh- Law ‘where the internal energy may be calelste from the ides lv as ik Solve forthe reactant and product internal energies. niin Sndly +O Rin) FE {Ug (mob {14917 ki/hgmet fact ~ 0 = (8.3143 kihgmo1-K)298°Ky 2 moll +0 ~ (8.3143 KU/RgMo-K)298" Ko, Ug = —82 350 ki/Agmol fact mi Ue nll +O — Fe) — RTI, U, = (1 mob) —393 757 Kikgmol fel +4008 kl/hgmol Fel ~ (8.3143 k/AgmoL-KY400" Kn, + (2 moh-241 971 kihgmol fal +3452 hemo fuel ~ (83143 KI /kammal-KW400°K co p= 876 764 kifkgmol fue} “The et tanster is @ The pressure may be found from the ideal-gas law applied to the reacta products Jy — Uy — Up~ Up =~ 794 414 kgm fuel and BF = na, Daly moRTy Divide one equation into the other and solve for p 1, _ QO.3 KPa) snoINS00°K) ina, GO m0298"K) men 136 kPa Comments: 1. The expression for the internal energy can be used only ithe substance isan ideal eas 2, Using the molalideal-gas Jaw with the universal ens constant allows ws to model reactants ind products with the same equation. Care must be taken to use the Appropriate number of moles for the reactant side and the product side. It is ‘unusual thatthe numbers of moles are equal =394 Coren 12 / REACTIVE SystEMS 12.8 ADIABATIC FLAME TEMPERATURE So far we have assumed that heat transfer and work oocur during a combustion process, no work, no heat transfer, and no change in kinetic or potential energy should occur, all the thermal energy would go into rising the temperature of the products of combustion. When the combustion is complete under these circu stances, the maximum amount of chemical energy has been converted into thermal energy aod the temperature ofthe products is tis maximum, This temperature is called the adiabatic fame temperature. ‘Should the combustion be incomplete or exces ait be use, the temperature of the mixture would be lessthan the maximum adiabatic fame temperature. Excess is used in engine design 10 keep the temperature within metallursies limits. f ‘combustion is incomplete, not all the chemical energy is converted into thermal energy; hence the temperature will be lower than the maximum that is possible. ‘When excess air isused, the thermal energy must be used 1o raise he temperature ofa treater mass; hence the temperature rise forthe fixed amount of thermal energy will rot be a5 great a the maximum, thd factor that reduces temperature is isso- ation of the combustion produets. The dissoeiation reaction is endothermic it "uses some of the available thermal energy to proceed. We will discuss this reaction later. ‘The following example calculates the adiabatie Name temperature, It is atrial and-errar process Example 12.11 Gaseous propane is burned with 100% and 400% theoretical air at: the adiabatic Name temperature in each case, °C: Determine Solution Giren: The complete oxidation of propane withspeciied smountsofthearetical ait 25°C Find: ‘The adiabatic flame temperature foreach cas. Assumptions: 1. The products and reactants behave like ideal eases 2. No work is dane 3. The heat transfer is zero, 44. The changes in kinetic and potential energies may be neglected, 5, The molal ratio of nitrogen to oxygen in air is 3.76 Analysts: The redetion equation balanced for 10% theoretical aie is CJH, + 50, + 5(3.76)N, + 300, + 4H,0 + 18.8%, 128 ADIABATIC LAME TEMPERATURE 395 Applying the frs-law equation with assumptions 2, 3, and 4 yields Has He Hg= Snlliz +0 ~ Fi Hg = 108 909);= 103 909 ktm ue Hp= Sy ndip + Oe ~ Fa y= 393 787 kikemol fuel + (i* — Fea)co,+ {241 971 K/kgmal fe + = Rigo * 18810" ~ Falk At this point the temperature of the produets must be guessed at. Assume that 7, 2500°K. Then p= + 10 845 k/kgmol fe and Hp~ Hy= +114 758 4/egmo fel “Try another temperature, 2300°K, for the products p= ~206 068 kl/kgel fas and iyp= Hy =~ 102159 khgmol fel Figure 12.7 shows a plo of (Hy-— Hg) versus: Where the line connecting the wo points intersects the (1, ~ H) = O axis isthe linear approximation ofthe empera- ture that will satisfy the frstlaw equation. The temperature that will balance the ‘equation is T= 2394°K, the adiahatie Name temperature for 100% theoretical at, ‘Now balance the combustion equation for 00% theoretical ai. CoH + (4NS10, + (AXSIB.76)N, + 300, + 4440+ 150, + 78.2; The fist law with assurmptions 2, 3, and 4 yields Hepa Hy and y= 1-103 908) Assume that T= 1000°R: hence p= +10 612 kifkamol fuel 103 909 ki/kgenol uel and 114521 ki/kgmol fuel Hy ~317 200 kl ego! fuel396 CHAPTER 12 / REACTIVE SrSTeMS Figure 12.7 Gragh for Example 12.1 and Hp ~ Hy =~213 381 kl/kgmol fuel From the plot in Figure 12.7, the value fr the adiabatic lame temperature is 942°K. for 400% theoretical ae Comments: |, Using excess ai brinas about a significant temperature decrease. This can be an important engineering tool in designing optimum energy transfer in equipment such as steam generatars and automotive engines. 2. The assumption of linear extrapolation between temperatures, wed in Figure 12.7 is reasonable ifthe temperature changes are not large. = 12.9 ENTHALPY OF COMBUSTION, HEAI 1G VALUE “The enthalpy of combustion, Ag, isthe difference between the enthalpies of the products and reactants at the same temperature, 7, and pressure. Thus fige=He— He Fine = S nfl + Gis — hii — dh; + hz Rigg], (12.12) i 129 ENTHALPY OF COMELSTON, HEATING VALUE 397 ‘The enthalpy ofcombusion usualy is expressed inthe units oiljoues per ioe gram of fuel. This i also called the heating value ofthe fuel at constant presue. Because the heat is ansfered at constant pressure in an open system ard seal 0 the same enthalpy ciferece, The enthalpy ofomfstion of vaous fuels sven ‘Table C3, where the vals ae given a he reference sate “The internal energy of combustion, iy, is the difference between the internal neces ofthe products and reactants and'may be wciten at figp™ Up~ Up Tay 5 nfs + Os fig) ~ RT ~ le + Fig) RT, (23) where al the reactantsand products have been considered as gases. Should this nat be the case, then pBmust be used inplace of RT inetermining the internal enersy. Since this sequal to the heat transfered at constant volume, the constant-volume heating ‘value of the fue isalso equal t0 gy. Note that equation (12.13) may bewnitten more ‘compactly as bw Ar(S0)-3) aC} ‘combustion is in the liquid or vapor phase. The higher heating value of a fuel Example 12.12 Calculate the enthalpy of combustion —the heating value—of liquid propane at 25°C when the water in the products is aliquid and isa vapor. The enthalpy of evaporation is 370 Kk Solution Given: The combustion oftiquid propane st 25°C with its enthalpy ofevaporation known, Find: The higher and lower values ofthe enthalpy of combustion, or the heating value, ofthe propane. Assumptions: |. Combustion iscomnlete and hoth reactantsand praduetsareat the sme temper ture 2. The ideal-gas law applies so gaseous reactants and produetsa8 Ccunrren 12 / REACTIVE systeNs Analysis: Write the balanced reaction equation with only oxygeo. Nitrogen is not ‘Included, as the temperature of productsand ceactants is thesamte and nitrogen is not dissociated. The enthalpy ofthe nitrogen, an element, is 7270 at 25°C. CyHyll) + 50, > 3C0, + 4H,011) From the definition of heating value, Fige= Hp Hy) ‘The enthalpy ofthe reactants is Thy, Ue snan = eg ~ Mh ~ 103 909 ~ 44.1(370) = ~ 120 226 KJ /kemol fuel For the product, enthalpy is Hyp= XY nizy y= 3 0, + Mi ns p= 4-395 737 + 4-286 010)= 328 311 kl/kgmal fuel The higher heating value, where the water is liquid, is Figen (2325 3+ 120-226 gm fuel) cs A kgikemol) For the casein which the water in the products remains a vapor, the enthalpy ofthe reactants s the same, but the enthalpy ofthe products is Hy=Sinfiy He = Foo, + 4 cx Hp = 3(-393 757) + 4(~241 971) Hy=—2 149 155 kI/kemol “The tower heating value of propane is Fog = C2189 155+ 120 226 tr hgmot fue ~~ (44.1 ke/kgmol) ‘Comment: Because the heating valuc is defined as the enthalpy difference between reactants and products at the same temperature elements that have the same coe ‘cient on each side ofthe action equation do not enter ina the energy ealculation. 50,002 ka/kg =46 007 Sake Example 12.13 {7 Caleulate the enthalpy of combustion of ethane, C;Hg, at SO0°K. Assume the aver- | age value of the specific het a constant pressure for ethane to be 2.22 ki/ke-K. 12.10 SECON! 1210 SECONOLAW ANALYSIS 399 Solution Given: “The combustion of ethane at 500°K and its specific heat at constant pres: Fin ‘The heating value, the enthalpy of combustion, of ethane at $00°K Assumptions 1. Ethane isan ideal gas, as sre the reactants and products 2. Only oxygen is needed to determine the combustion reaction, as nitrogen woul hhave the stme velue on both sides ofthe eaction equation. Analyses The balanced reaction equation is CH, + 3:50, 200, + 31,00) The definition ofthe heating value is igp~ Hp ~ Hat the same temperatute, The enthalpy of the products is y= Dall (393 757 + 8314) + 30-241 971 + 6920) = ~1 476.039 kl/hamel fuel Incalculating the enthalpy ofthe reactants, the enthalpy ofthe change ofethane from 208°K sé, T — 298), found from the ideal-gas equation ftateforenthalpy change, The reactnt enthalpy is Hem Srdlj + 05 — id +55— hl Hg = ME-84 718 ki/hkgmol + (2.22 Wi/kg-K) (30.07 kg/kgmol(S00 ~ 298*K)] + 3.5(6088 kI/kemol) By = ~49 925 kl/kgmal fuel The enthalpy of combustion of ethane is Fog (17H 089 + 49 925 kha! fued coe (3007 Faykamo}) Comment: When determining the heating value ofa substance at other than 25°C, the enthalpy change of that substance to the desired temperature, 500°K in this ‘example, must be included, This ofen involves nding the specie heat a sub stance as illustrated, a 7426 KPA AW ANALYSIS “The combustion prooess and most chemical reactions proceed very rapidly. As we have soon previously, processes that proceed rapa do so ireversbly, The entropy ‘haner for sich n reaction indivates how irmversihly the reaction occurred, and ‘nowsing this, we ean determine the available portion ofthe thermal energy released by the combustion process00 AAs with enthapy, we must be able 10 sefer all the substance entropies t0 a ‘common reference state or base. In this manner entropiesof different substances may be added anc subteacted, since they are common tothe same base. The third aw of | ‘theemodynamics states thatthe entropy of al pure substances is zero at zero degrees absolute. Thisives usa reference base and entropy measure trom this base iscalled Gasoite eviropy. I Tables C.1 and €.2 the values of absolute enteopy at 1 atm pressure, 5° are given or various temperatures for several substances, In hese tables land by customary practice, | atm is essentially 100 kPa “To account forthe eacton’s not occuring at standard conditions, the absolute eteopy at somie sate 2is where Aj, isthe dlference berween theabsolureentropy at reference conditions and ‘he absolute entropy at sate 2. Foran ideal ss. By — Rint pro) the pressure is expressed in atmospheres, further simplifeations are possible. At reference conditions py = | atm; thus, re G,~ Rian) ~ i) Note that {y~ dy which allows us to write 3,— Rinony ‘or in general B- Fini) (25) [values of 6 are not available in the gas tables, then fc, T/T rust be evaluated, In Chapter 9 we studied available energy and introduced the concept of aail- abi, We mentioned that availability was panicularly important when dealing ‘with chemical reactions. Furthermore, we shoved that the change of availability was ‘equal to the mayimuma work posible fora process between two states, and that if this process cook place at constant temperature and pressure the change in availablity ‘was equal to the change in the Gibbs function, ds (dO (216) le we integrate this expression betwen inital and final eonditions, then E- Dus (247 Wu ay = 3 sity, The availability deereases ‘where the maximum work is written asa positive a between the initial and final conditions. 1210 SECONDLAW ANALYSIS 404 Since p= A= Ts and T= To, then for the reactive systems under eon sideration grh= Ts Just senha of formation was necessary when analyzing compounds in sta ‘analysis of eeactive systems, ss the Gibbs function of formation, &, necessary in Secondsiawanalyis. The Gs function of formation isgvenin Table: Torseveral Compounds a reference conditions of 25°C and | atm presire. The Gib fune- tion oF all elements zero at reference condiors. The allowing example ilu teats this Example 12.14 Determine the Gibbs function of HO) at 25°C and | atm Solution Given: The oxidation of hydrogen with oxygen to form liquid water at 28°C and Yatm, Find: ‘The Gibbs function of liquid wate. Assumptions: 1. The gases in the combustion equation behave like ideal eases. 2. All the water Formed is liquid Analysis: The balanced reaction equation is 2H + 0,-+ 2H,001) ‘The difference i the Gib function forthe reactants and products: Gp Gp=(Hp~ Ha) TdSp~ Se) G p= Ga= EZ nsipy— Yb, ] Since the emhalpy and the enthalpy of formation of elements are zero at 25°C and ~ 16 B ncins~ Bmsoz cuapree 12 /REACTHE sysTENS 1am, he deren in the Gis action x Gp Gy 209 ~ 80H 25 Pod Gp~ Gy= (2 moles\—286 010 k3/kamol) ~ (298°K (2 motes} 69.980 KI /hgmol-K) = (2 moles(130.684 by /kgmol-K) (1 moe(205.142 Mi/kemol-K) 478 708 Ki/kgmol GG “The Gibbs function of formation ofall clements i 270, Bence Gy= 0 and the dirence isthe Gibos function of produots Gp = ~474708 for 2 stl 110. Baayy = —287 384 Khao se 6p= 2B ow example 12.15. Propane at 25°C and 1 atm is burned with 400% theoretical airat 25°C and | atm, ‘The reaction takes place adiabatically, and all the products leave at Latm. The ‘temperature of the surroundings is 25°C. Campute the enteopy change and the © maximum work and compare these to values from an isothermal reaction, Soltion Given: The adiabatic combustion of propane with 400% theoretical air with initial emperature and presse given a8 well asthe final pressure. Find: The entzopy change and the roaximum work for adiabatic and isothermal ‘combustion, Sketch and Given Data: Flawe 128 Assumptions 1. The combustion is complete 2, The molal ratio of nitrogen to oxygen in ai is 3.76, 3. The reactants and nroduets behave lke ideal gases 4, The changes in kinetic and potential energies may be neglected. 1210 SECONDLAW ANALYSIS 403 Analysis: The balanced combustion equation is Cay + 4(5)05 + (ANSI, 26)Ng + 3CO, + 41,0 + 150; + 75.2Ns Whe reution is adiabatic, the temperature of products sequal the adiabatic fame temperature This was calculated in Example 12.11 to be 942°K, The entropy of Droduets and reactants may now be calculated. Se= SG ~ Cn + 2058, + TSAR aoe 1270.09 kd/kemol-K) + 20(205,142 kikgmal-K) + 15.2(181.611 ki/kgmolK) ‘Sy 18.782 ki/kamol fue-K Sp= Dna = Biko, + Shia + 18%, + 75.256 her Sp 5126.04 ki/kamol-K) + 4(230.22 ki/kpmol-K) “+ 15(241.47 KI/Agmol-K) + 75.2(226.19 Ki/kemol-K) Sp 22.351 ki/kgmol fuelK “The iroveribility, J 6 To(Sp~ Se) 7 (298°K)22 381 ~ 18 782 kifkemol fe) 1.063 562 KI/kgmo fel “The maximum work for this case may be found by finding the change inthe avail- ability of the reactants and products. The Gibbs function is tabulated only for refer fence conditions, soit cannot be used inthis situation, © 2 Ga Gp = (Hy ~ ToS) — Ue TS) Since the temperature isthe adiahatie ame temperature, Hy = Hp. The maxirnum ‘work reduces to ae (Sp Se) 1 063 562 KI/hgmol fuel 1063 562 k/kgmo! fuel) ‘on = (441099 Kakgmol fuel = 246 117 Wik fuel “Thisrepresens the maximum possible work an engine could pexforrs ithe products ‘ol cannbustion were at 942°K. For en isothermal reaction, we may find the maxi rum work by finding the change inthe Gibbs funetion between the reactants anc.Ccoamnen 12 / active sysenes Drodvets at 25°C and | atm pressure Wea = Ga~ Ge= ¥ nidt ~ Z m8) Gym (23.502) +040 p= 394.631) + 4— = =2 133 201 ki/kpmol foe! an = 47 BAD Keg fuel 23 502 ki/kymot fuel STEN +O+O Comment: ‘The isothermal maximum work represents the ideal energy available from the combustion reaction to do work, Ifwe find the aetual work that an engine docs using the combustion proces asthe enery source (such asan internal combus- tion engise) and compare the two, we can determine the efficiency ofthe engine. [Actually the heating vale ofthe fuel, aot the change the Gibbs function isused in current engineering practice, a Example 12.15 assumesal the products et at | atm pressure. Actually, the total pressures constantand isthe sum of the partial pressures ofall the constituents. The following example illustrates this more realistic situation. Example 12.16 Propane reacts with 400% theoretical air in an isotherms! reaction where the inital and final conditions are 25°C and 1 atm pressure. The surroundings temperature is also 25°C. Determine the maximum work, Solution Given: Propane oxidizing with 400% theoretical ar in an isothermal reaction 25°C and | atm pressue, Find: The maximum work ‘Sketch ond Given Datas Figure 129 12 10 sEcowDLaW aNALYSS as Assumptions: 1, Reactants and products behave like ideal gases, 2. The mot eat of nitcogen to oxygen in ai is 3.76 The changes in kinetic and potential energies may be neglected. Analysis: Tee combustion equation is CyB +200, + 152%, > (0,4 4H,0 + 150, + 75.2N: “Te values of entropy must he ealeulated forthe partial pressure at whic they exis, j ~Rin(4) ‘The reaction is isothermal, 0 the temperaturetcrm in the entropy equation adds out ‘The panial pressure af the ‘th component is msn were ys the mole fraction of the ith component, Thus, verete(!) Note that 1/9, = ninyand R= 8.3143 ki/kgmolK. For the veactants GH, 1962 «37967 2700S s0BUR Or 13059 osts2 e207 N32 Ls 2m46T9HBLT 193.55 92 For the products Co, 3d DRONE LTO HO 24326528 188833 o: 1s317 208142 N 2130191611, Tae maximum work is equal tothe change inthe Gibbs fonetion or expressed in tems of enthalpy and entropy as406 CHAPTER 12 / REACTIVE STEN Wan Ha By ~ ToS Sd Hy= ES mlij +h 1103 909 Ks /kamod) + = 54 + 4h, Hp= 3-393 757 KI/KEMOD co, +4-241 971 KU kpmodyyo + 0+ 0 —2 149 158 ki/kgmol fue! Hy~ Hy +2 045 246 k8/kgmol fuel Seo Ei Sp 108.032 ki /emol-K) + 20(218.201 Kl/kamol-K) + 75.2193.687 KU/Agmol) = 19 235.1 kifkgmo fuel-K Se EN5 s, = i 103 909 ky/kemot fue & " 3(242.713 kl/kemol-K) ++ 4(215.359 KI/Agmol-K) + 15(220.679 ki/hgmoF-K) + 75.2(193.741 kl/hgmol-K) ~ 19 469.1 kkgmol fuel-K TAS ~ Sp) = (298°K(19235.1 ~ 19469.1 kifkgmno fuel-K) = 69 752 kkemol fuel Wag = 2.045 246 + 69 732-= 2 114 978 kI/gmol fuel (2.114978 Ki/kgmol fuel) ‘se (445099 barker fuel) ‘Comment: “The value forthe work including the pressure is esentially the same as ‘when the pressure effect was neglected in the previous example, ‘Thus, unless the Uesired accuracy of the peeblem demands i, we wil not include the pressure effet. ‘This sort of eect would e included in precise scientific measurements an calcul tions. = 960 ke fe 12.11 CHEMICAL EQUILIBRIUM AND DISSOCIATION “Thus far in considering chemical reactions we have considered complete reactions, ‘bat this isnot the whole picture, In considering thermodynamic equilibrium, we ‘concentrated on thermal and meshanical equilibrium. Likewise, in studying chemi 12:11 CHEMICAL EQULISRIUM AND DASOCIATION 407 cal reactions, we must study chemical equilibrium, The following discussion isby no means as extensive as would be found in a textbook on chemical engineering ther- ‘modynarics Asa reaction proceeds, some ofthe produ dissociate into the orginal reac- tants when chemical equilteium is reached, the reaction is proceeding in both directions s9 there is no net change in ether the reactants or the products. This reaction may be written as WAFWBH + YX tyYS 92:16) where isthe stoichiometsic coefficient for the balanced reaction equation, and B arethe reactants, and X and ¥ arethe products. The diference betseen the moles OF i, and ¥, its stoichiometric coefficient, is that 7, refers to the moles available, ‘whereas ¥, denotes the equation requirements iow can we determine when chemical equilibrium has been achieved? When a system sin equilibrium, it can no longer produce work, The Gibls function ean e tsed to determine the maximum work of a system at constant temperature and pressure. Thus, by determining the Gibbs function ofthe reactants and of the pro tels, we oan determine whether at not a chemical reaction can occur. When the Gibbs functions ofthe reactants snd products are equal, na work may be done and chemical equilibrium is achieved, ot (dG\yg~0 (219) for chemical equilibsium. tis possible to show that the change in the Gibbs function a constant tempers ture and pressure is the criterion for chemical equilibrium without use of the ‘maximum work concept Heretofore the Gibbs function has been written for a single species; however, be systems of many species we may write that Gace am sant 220 ae ~(22) ap+ (#2) (2). em won (22), aro ($2) ores (22) an ona ‘0 ec) _ aT) an tnequation (1222). 8th hemi potenti ofthe th component. The chee potential of species / 6 the driving force in changing the moles of species i Tet usapply the change ofthe Gibbs function tothe reaction in equation (12.18),408 Ccuabren 12 / EACTE Syste cewuing at constant emperor ana ress (Oday = Sd . (12.23) (dG) Ha dig + iy tg * a By The changes in mole numbers are dependent on one another, since the products come from the reactants. Assume a farward reaction —the lefi-hand side is being pleted —and let us further assume an infinitesimal change, soa proportionality tonstant may’ Be used To describe the change in the mole numbers. Thus, ky dngathy, — dny=the, (12.28) ‘The negative and positive values of & reflect the depletion and gain of species, Equation (12.23) becomes (dng = (ita — Bats Hatt He (225) Since weare interested in chemical equilibrium, assume that the small change ecurs at the point of equilbyium where (d6)¢, = 0. Thos, Hale S86 Hale (12.26) for chemical eauilibriue. “The concept of work may be related to equation (12.23) by recalling equation (6.21), where work is defined as an intensive property acting on the change of its related extensive property ‘Consider a system containing methane and oxygen, existing atthe same temper- atuce and pressure asthe surroundings. The system is in mechanical and thermal ‘quiltrium, Is i in chemical equilisrium? No, because if we computed the Gibbs function for the reaction, we Would find that Gy > Gy, $0 a reaction could occur. [Nothing will happen, however, until 2 spark is introduced into the mixture. Then a reaction will oceur until Gy = G,. Thus, We find that the Gia function has two purposes 1. It tells us whether or nota reaction can oveur Ifa system is in chemical cquilibrium, (dG)rg = 0, no reaction can occur. 2, Tisthe thermodynamic potential that cause the constant-temperature and cconsiantpresure Feation (9 occur. Tt does not tellus how fast the reaction ‘will oscur. ‘Consider the reaction AE RBS RX NY (227 an let the reactants A and B low slowly into aoxso thei relative amounts remain ‘constant, reaction takes place, and products X and Y are formed, We will prescribe that theamaunts ofthe products nem are proportional theamountsat And R, nd that the ratio ofthe mols of the products to the moles of the reactants is Constant. Forthistooccur, products X and Y must beremoved from theboxin such 12.17 CHEMICAL EQULIBRUM AND DISCCIATION 408 gure 12.10 Van" Hof equim box. manner that the mass entering the box equals the mass leaving. The reactants and products leave at the same temperature and pressure, andthe easton also occursat histemperature This iscalleda Van! Hoff equilibrium Box. Figure 1210ilustrates this proces. Since the Gibbs function isused in determining chemical equilibrium, let usfind the Gibbs funetion foreach ofthe substances inthe box. aG=V dp Sar ForT=6 dG~Vdp Foran ideal gs, = nip ag= nar 2 > Inverating, (G-G)= nn (2) (228 Wethen apply equation (12.28) to the conditions inthe bos. We let = the panda posure ofthe iven component inthe box. Thus, for component A (u— Gade = 0RTID (8) (12.298) where is the total pressure. ‘Similarly, expresions may be written forthe other substances, For substance B, rn (2) (22% 7 (Ga, ~ Ged For substance X, sien miitin( 2) (12.50 - (x, 290)a0 Ccuaprer 12 /REACTE SYSTEMS Adding equation (12.288) t0 (12.294) yields (G+ Gadr~ (Gy, + Gar + Gx, + Gye = (Gx, + Gr ~nirin()+mirin()+nkrm(2) (230) =n trin(2) Since equilibrium conditions exist within the box, the sum ofthe Gibbs funetion ofthe reactants must equal the sm ofthe Gibbs functions ofthe products in the box, Hence (Gn * Gur Cu Gedy =O can Combining equations (12.30) and (12.31), Tan 2) oer orn (2) sr (2)P ‘We let the total pressure, p, equal 1 atm and express the partial pressures in atmospheres. Simplifications result ifthe pressures ae so expressed (Gp Gade RF In (p3Ye RT In l= Rin (p,y~ RT In (Br Gy Gaie~ RW rin (#22) (2a P35 is defined as ‘The equilibrium constant, (1233) ‘Thus, equation (12.32) becomes (G,~ Gar + RTINK) is @ constant only fora given temperature for an idea gas. Values forthe natural Jog of the equilisium constant K, are given in Table C.4 ‘When the temperature ofa gas i increased, there isa tendeney for the gas to sissocate, So at any temperature theres an equilibrium mixture ofthe gas and its dissociated products. The dissociation process is endothermic and, as uch, tends to reduce the total energy of system to minimum value fora given temperature, The cect of dissociation reduces the adiabatic fame temperature, as some of the chem cal energy is used in the dissociation process instead of raising the thermal enetgy The fallowing examples illustrate the effet af dissociation, example 12.17 Determine the percemage of dissociation of carbon dioxide into carbon monoxide find oxygen at 3800°K and 1 atm pressure, ~~ ca 12.11 CHEMICAL EQUILIBRIUM AND DISOCIATION 411 Soluson Given: Te dissociation reaction of carbon dioxide into carbon monoxide and oxygen ata given temperature and pressure Find: The percentage of dissociation. Assumption: Reactants and products behave like ideal goss, ‘Analysis: From Table C.4 the In (K,) ~ 1.170 forthe reaction CO + 10, —> CO, Let x denote the dissociation of 1 ml of carbon dioxide. The reaction equation is xco+S0,=(1 = KO, “The total number of moles present a equilibrium is(2-+ x2. The partial pressare foreach component, may'be expressed in terms ofthe mole fraction and ihe ota pressure, ‘Since the total pressure is 1 atm, we may solve equation (12.33) for the eoulibrium constant, K,, 2 Plo 2 =) Tabor we Solve this equation for by atriakand-error process, knowing that In (K,) = 1170. S=O3 Ky= 646 In(K)= 1865 xn 04 Ky= 3673 In(K)= 1.201 ye0425 Kj=32 In(Ky= 11 “Thus 42.5% ofthe carbon dioxide has dissociated at 3800°K, Comment: The dissociation reaction uses some of the chemical enereyceleased by ‘combustion and thus reduces the adiabatic Name temperature. In deters he ‘adiabatic flame temperature, we must find the amount of dissociation before eau lating the enthalpy fa442 cuapten 12 eacive systems Example 12.18 Hydrogen is burned steadily with 100% theoretical airat | atm pressure and standard temperature. Determine the adiabatic flame temperatuee and the maximum tem- perature, taking the dissociation of H,O into H, and O; into account, Solution Given: The steady-state oxidation of hydrogen with air for adiabatic conditions ‘with knowin initial conditions. Find: The maximum temperature possible with and without dissociation occur sing Assumptions: 4. The reactants and products behave lik ideal gases 2. The work and heat are zero, ‘The changes in kinetic and potential energies may be neplected. Analysis: The combustion equation forthe oxidation of hydrogen is 11, $0.50, + 1.88N, + H,0+ L.88N, The adiabatic flame temperature occurs when Hl, = Hp. In this ease, the reactant emihalpy is zet0, a5 the fuel is hydrogen, an element” Following the techniques escribed in Example 12.1], determine the adiabatic Name temperature to be 2528°K, Trae combustion equation accounting fr dissociation of water inthe products of combustion is Hy +050,+ L88N) +1 98,04 stt,+ 5 0, + L88N; where isthe faction of water that dissociates 1, Firstaw analysis y= He H,=0 2. Guess a temperature: look up In (Kp) 13, Guess value for = ealeulate K,—the correct value of s will lave the samme value ofl (&,) as in step 2. po ne 12:11 CHEMICAL EQUUIBRUM AND DSSOCITON 413 4. Using the value of found in step 3, calelate#, for feslaw analysis 5. Repeat steps 2-4 until fp = Hy. Guess T= 2200 K: ozotix fe“ Tyage +0507 ba nous Dos nooss 502 90120 ‘Assume x ~ 0402 forthe inital calculation: the products side of the combustion equation is 0.98H,0 + 0024, + 0.010, + 188N: Guess T= 2400°K: Ink, [A value of = 0,04 balances ln (K;) and yields Hp= ~$302 Git, Hig versus Ts the lie intersects (Hp ~ Hy) = Oat T= 048 esgetially balances the frs-la equation, Thus, 4.5% of the water aisociate, lowering the maxloum temperate by 92°K, =5.025 kemol fuel. Plot 3K. The value ofaa ‘CuapTen 12 /RERCIVE SYSTENS Comment: Inhyérocarbon combustion the dissociation of the hydrocarbon should beconsidered, aswell asthe reaction of nitrogen and oxygen to form nit oxideand the dissociation of other products, Allo these reactions are endothermic, tending to reduce the products’ temperature = In Example 12.18 only one dissociation reaction is considered, A number of other possible reactions could be also be considered. One such reaction isthe dissoci- ation of water into hydrogen and hydroxyl. As additional eactions are considered, auditional unknowns are added, and the problem solution becomes more compli tated, Solving a problem with more than one dissociation equation without a com- puler isa daunting proposition, The TK Solver model COMBUST.TK solves com- bustion process problems invalving up to three dissociation rections: water into hydrogen and oxygen, water into hydrogen and hydrox and carbon dioxide into ‘earbon nionoxide and oxygen. COMBUST.TK containsdata on ideal-gasemthalpies from Table C.2 and equilibrium constants from Table C.4 Example 12.19 Repeat Example 12.18 using COMBUST.TK and assuming the reaction products are only onygen, nitrogen, water, hydrogen, and hydeoxs! Solution Given: The steady-state oxidation of hydrogen with air for adiabatic conditions with known initial conditions. Find: The maximum temperature possible with dissociation of water taken into Assumption 1. The reactants and products behave lke ideal ses 2. The work and heat are zero 53. The changes in kinctic and potential energies may be neglected 4. Two dissociation reations will be considered, HOH, +050, and H,O-+0.5H,+0H Analysis: Load COMBUST-TK into TK Solver. In the Variable Sheet, enter the enthalpy of formation of te fuel, ine temperature ofthe reactants, the pressure ofthe combustion process, the percentage of theoretical oxygen, the theoretical moles of / 12:7 @EMICAL EQULRAUR AND OSSOCIATION 415 ‘oxygen required per mole of fuel, and the theoretical moles of carbon dioxide and Avater produced per mole of fuel, Note thatthe last sree values come from the halanced eeaction equation without dissociation. The solved Variable Sheet should Took like this: Comments Considering the dissociation of water into hydrogen and hydroxyl as ‘wellas hydrogen and oxygen resoltsin an adiabatic Tame temperature of 403.56°K, pout 30°K lower than ae caleulated in Exsnsple 12.18. Theadditional disocation Of water results in Further lowering ofthe produets’ temperature ze416 CHARTER 12 / REACTIVE Syste 12.12 STEAM GENERATOR EFFI CY ‘The fst-Law efciency of any device is output divided by input. This sno exception for steam generators, Theonly question to he answered is what we defineasinputand ‘output water/steam aevoss steam generator ‘enerky supplied by fuel (234) “The eneray supplied 10 the water is the change of enthalpy of the water from the feedwater entering to the superheated steam leaving, All lows must be considered if some ofthe seam is extracted before entering the superheater. The energy supplied by the fuel is the fuel How rate times the fuels higher heating value. ‘A power plant's efcieney is also denoted by its specific fuel consumption and hea rate. The specific fuel consumption, sf, is eral 123) Wey kw Lape The difficulty with using equation (12.38) i that it daes mot account forthe fuel’s -ncating value In comparing plant and/or steam generator designs, we should know ‘the heating value ofthe fuel, The heat rate eliminates this problem, and modern convention recommends its use over spevfc fuel consumption; thats, ge A ae Woe EW Linpehe J Heat rate 12.43 FUEL CELLS A fuel cell transtorms chemical energy into eletrical energy through a series of| catalystaided oxygen-reduction reactions. Unlike many energy conversion systems such a the steam power plant and the internal-combustion engine, the Ful cell enerates electricity ina continuous and direct proces. I this manner, the excessive losses that aecur in multistep energy conversion systems may be avoided using & single-step process. Thus, fuel els tend to have higher theoretical energy conversion efficiencies ‘The uel ellis composed of anlectrolyte sandwiched between electrodesknown asthe anode and catnode, as shown in Figure 12.11. Unlike the conventional battery hovsever the ful celleonsumesexternally supplied fees, The uel suchas hydrogen) and the oxidizer (normally oxygen in the form of ai) are supplied 10 the anadic and cathodic sides ofthe cell, respectively. The electzochemical eaction between taese {results inthe cranster to electrons and the production ofa voltage between the two electrodes. When a loadisconnected in series to these electrodes, current calculable bby Ohm’ law, will result. The theoretical voltages that arise Teor these fuel cell reactions normally range between 1. and 1.3 V de at (-2 kW? of electrode. Asan example, let us analyze the most common fuel cell, the hydrogen-oxyget 4 pen ik wag cus 497 I 1% i Figure 12.1 Fuel cl fuel el, Fuel as hydrogen enters the fuel celland loses an electron giving the anodic plate a negative charge, The hal-cell reaction forthe anode is Anode + H,(g) (anode + 22°) + 2H° Atte cathe, the oxygen molecules supplied by theair pick upelectrons giving that plate a positive charge. The half-cell reaction forthe cathode is (Cathode + 2¢°) + 4O,(g) + 2H* -> 1,00) + cathode When a load is connected in series with the electrodes, a current develops as a fanction ofthe induced voltage. The excesselectzons in the anode travel through the Toad tothe cathode providing power. The H* ions formed at the anode according to the hal-cell reaction migrate through the electrolyte solution to the cathode, The foxygen then combines withthe 11 ions to form water “Thermal efficiency is typically defined to measure the performance of « heat engine. Because the performance ofa fuel cll cannot be defined by heat and work48 transfers, “fu! cell ficiency” ean be defined as maximum work __ AG "e~ Change of overall enthalpy ~ ATF (1237) where AG equals the change the Gibbs function and A 7 thechangein enthalpy I is important not to confuse this wth thermal eficiency for heat engines, asthe 60 ‘cannot be directly compared. The Gibbs function is defined as G HTS ‘Therefore, at standard temperature and pressure (25°C, 1 atm) AG =G,- Gy H,— Hy) = TdS,- So) Bua. ay nj 26° = Jnl, “The values of f and s for substances are found in Tables C.1 and €.2. Ta simplify calculations, the hyerogen-oxygen fuel cell reaction may be written Hig) +4049) > 4,00) Calculate the change inthe Gibbs function a: standard temperature and pressure, substituting the tabulated values, The Gibbs funetion of an element is zero at stan= dard conditions: thus, Gis 270 and Gr ip“ og = ~237 327 KUkgmol “The ehange in enthalpy fr he overall cell ection is I= 15, =O yy = ~286 010 KIgn0l ‘The ideal hydrogen-onygen Fue cell efficiency is p= 083 oF 83% “The fuel cll voltae is found from AG =—ne0 (123) ‘where AG is the change in Gibbs funetion per mole of fuel,» Js the number fof electrons translerted per molecule of fusl, 18 Faraday"s constant, 96 500 KV —kemol, and 1s the fel cel voltage anes TAOLE 122, THEORETICAL (UEL CELL PrAFORMANCE ul eatresction File) $04@) =H.) wisn cs 419 Tante/egroh 8 (ere eM reer 5010 Atk “ a da tose 1.0) a i tee mast ‘ A a Biss 8 Love Coxe) ” saa ei 23161 es 9m) se A itork we GS) at tan se FO) — COM ' a Aor Si Beh ties tits Tb) 3COWW+ HL Le es sassy 358s tant Simm es Oe Hence “A cumber of other fuels may be used in fuel eels, some of which are fisted in ‘Table (22. Each ofthese fuels reacts and may be analyzed ina similar fashion. The fuel eel eaction for carbon monoxide Tue is cove) + 0x8) COME) To calculate ac He Hy) -,doesnarequal zero because eg ust beincluded init Sia Goes ot chal zero, Substituting, we ind that AG" = Gy Ge 93 757 ~ (110396) ~ 2991213.795 ~ 197.653 ~4205.142)]= 257 405 xa/kgmol20 CHAPTER 12 / REACTIVE SySTENS ‘The change of enthalpy for the fuel cell reaction is AH=H,-H, AH = ~393 757 110596) = 283 161 Ki/ksmol “The Fue cll efficiency is ac Ne BHT Tags Ter 0907 oF 909% and the fue cell voltage is +257 405 Pe aging = 355500) = 153 “The fuel cell efficieney and voltage may be calculated at other than standard conditions. Consider the carbon monoxide fuel cell at 1000°K and } atm pressure. 0 {3 ally + = foh Bally + ou} -7[za6-ga] 86 = [393157 439405) — (10 595 +21 66 8 emo) = 0.5(22 707 kgm) ~ 10001269 25 ~ 234531 = 05248.585 hemody g-=~195 797 B/Kgmol “The change in the fue cell enthalpy is AH =—282 796 Ki/kgmol. The fuel cell ficiency 8G _=195797 ie and the fuel cell voltage is AG | +195797 nF (296 500) ‘As may be sen in Table 12.2, some deat fuel cll eficiencies may exceed unity ‘These cases correspand to processes in which the fuel eell absorbs heat from the surroundings. In actual fue} cell operation, losses occucring during electron transfer at the leetrade, during mass transport through concentration gradients, and during elec- {yon transpor through the electrolyte raul in ence lores that may exceed 25% of the ideal encray generated. Lo peostews gt) 421 CONCEPT QUESTIONS CONCEPT QUESTIONS 0 Does the presence of nitrogen in air alle! the combustion proces? How? ‘What fer doos the water vapor in air have on the com What ic the dow point temperature? How i this determined? Describe the arf ratio Isthe aire tio on the mass and mole tis the san’ Can water be we 6a fel in a combustion proces” What ate difrenes between systems where reactions oseur and those where none 8, Will mixing fol with oxpgen Be sulfcient 1 sata combustion process? 9, Whatis “ences ir"? 10. Is thee cierece beeen complete contusion an hear ion 0c 11, Deseribe the wie ofan Ora analyze. Whats meant by "sy bass” 12, What isthe heating vale of ae? 13, What causes the munsssl differences heoneen Niger and lower hesting values of fuels 14, Whatisthedifeense between theeatalpyofcombustion and the enthalpy of formation? 15, Whatisan eatothermic eation? An exocnermic react 16, What ithe aati Dame temperature? How are the entropy values of gases ater than Lamy pressure determined? 18, Whats the value in determining the Gibbs Funetio of irmation ofa compound? 19, Wha; charucteizes chemical equips’? 20, Will ful bura more completely at 2000°K or at 3000°K2 Why 21, Whats she energy conversion process in a fe ell? 2, Why ithe cl elcincy of some fuel cells greater than one? PROBLEMS (5!) sith 20 exoes aie Determine eric analss of roduc oF 124 Atul mineureofS0%/CyH,,and50% Cys oie {Gh the mas irene for $0 bg of Tuc: (B} ee ‘seas turbine powerplant receives an unknown typeof hysroeatbon fel. Some of te fuel sbuened with airing te following Oral aalsis athe products of

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