Solution Manual Engineering and Chemical Thermodynamics 2nd Edition By Milo D. Koretsky PDF

Engineering and Chemical Thermodynamics 2nd Edition By Milo D. Koretsky Solution Manual Table of Contents CHAPTER 1 Measured Thermodynamic Properties and Other Basic Concepts 1 Learning Objectives 1 1.1 Thermodynamics 2 1.2 Preliminary Concepts—The Language of Thermo 3 Thermodynamic Systems 3 Properties 4 Processes 5 Hypothetical Paths 6 Phases of Matter 6 Length Scales 6 Units 7 1.3 Measured Thermodynamic Properties 7 Volume (Extensive or Intensive) 7 Temperature (Intensive) 8 Pressure (Intensive) 11 The Ideal Gas 13 1.4 Equilibrium 15 Types of Equilibrium 15 Molecular View of Equilibrium 16 1.5 Independent and Dependent Thermodynamic Properties 17 The State Postulate 17 Gibbs Phase Rule 18 1.6 The PʋT Surface and Its Projections for Pure Substances 20 Changes of State During a Process 22 Saturation Pressure vs. Vapor Pressure 23 The Critical Point 24 1.7 Thermodynamic Property Tables 26 1.8 Summary 30 1.9 Problems 31 Conceptual Problems 31 Numerical Problems 34 CHAPTER 2 The First Law of Thermodynamics 36 Learning Objectives 36 2.1 The First Law of Thermodynamics 37 Forms of Energy 37 Ways We Observe Changes in U 39 Internal Energy of an Ideal Gas 40 Work and Heat: Transfer of Energy Between the System and the Surroundings 42 2.2 Construction of Hypothetical Paths 46 2.3 Reversible and Irreversible Processes 48 Reversible Processes 48 Irreversible Processes 48 Efficiency 55 2.4 The First Law of Thermodynamics for Closed Systems 55 Integral Balances 55 Differential Balances 57 2.5 The First Law of Thermodynamics for Open Systems 60 Material Balance 60 Flow Work 60 Enthalpy 62 Steady-State Energy Balances 62 Transient Energy Balance 63 2.6ThermochemicalData For U and H 67 Heat Capacity: cʋ and cP 67 Latent Heats 76 Enthalpy of Reactions 80 2.7 Reversible Processes in Closed Systems 92 Reversible, Isothermal Expansion (Compression) 92 Adiabatic Expansion (Compression) with Constant Heat Capacity 93 Summary 95 2.8 Open-System Energy Balances on Process Equipment 95 Nozzles and Diffusers 96 Turbines and Pumps (or Compressors) 97 Heat Exchangers 98 Throttling Devices 101 2.9 Thermodynamic Cycles and the Carnot Cycle 102 Efficiency 104 2.10 Summary 108 2.11 Problems 110 Conceptual Problems 110 Numerical Problems 113 CHAPTER 3 Entropy and the Second Law Of Thermodynamics 127 Learning Objectives 127 3.1 Directionality of Processes/Spontaneity 128 3.2 Reversible and Irreversible Processes (Revisited) and their Relationship to Directionality 129 3.3 Entropy, the Thermodynamic Property 131 3.4 The Second Law of Thermodynamics 140 3.5 Other Common Statements of the Second Law of Thermodynamics 142 3.6 The Second Law of Thermodynamics for Closed and Open Systems 143 Calculation of Δs for Closed Systems 143 Calculation of Δs for Open Systems 147 3.7 Calculation of Δs for an Ideal Gas 151 3.8 The Mechanical Energy Balance and the Bernoulli Equation 160 3.9 Vapor-Compression Power and Refrigeration Cycles 164 The Rankine Cycle 164 The Vapor-Compression Refrigeration Cycle 169 3.10 Exergy (Availability) Analysis 172 Exergy 173 Exthalpy—Flow Exergy in Open Systems 178 3.11 Molecular View of Entropy 182 Maximizing Molecular Confi gurations over Space 185 Maximizing Molecular Confi gurations over Energy 186 3.12 Summary 190 3.13 Problems 191 Conceptual Problems 191 Numerical Problems 195 CHAPTER 4 Equations of State and Intermolecular Forces 209 Learning Objectives 209 4.1 Introduction 210 Motivation 210 The Ideal Gas 211 4.2 Intermolecular Forces 211 Internal (Molecular) Energy 211 The Electric Nature of Atoms and Molecules 212 Attractive Forces 213 Intermolecular Potential Functions and Repulsive Forces 223 Principle of Corresponding States 226 Chemical Forces 228 4.3 Equations of State 232 The van der Waals Equation of State 232 Cubic Equations of State (General) 238 The Virial Equation of State 240 Equations of State for Liquids and Solids 245 4.4 Generalized Compressibility Charts 246 4.5 Determination of Parameters for Mixtures 249 Cubic Equations of State 250 Virial Equation of State 251 Corresponding States 252 4.6 Summary 254 4.7 Problems 255 Conceptual Problems 255 Numerical Problems 257 CHAPTER 5 The Thermodynamic Web 265 Learning Objectives 265 5.1 Types of Thermodynamic Properties 265 Measured Properties 265 Fundamental Properties 266 Derived Thermodynamic Properties 266 5.2 Thermodynamic Property Relationships 267 Dependent and Independent Properties 267 Hypothetical Paths (revisited) 268 Fundamental Property Relations 269 Maxwell Relations 271 Other Useful Mathematical Relations 272 Using the Thermodynamic Web to Access Reported Data 273 5.3 Calculation of Fundamental and Derived Properties Using Equations of State and Other Measured Quantities 276 Relation of ds in Terms of Independent Properties T and ʋ and Independent Properties T and P 276 Relation of du in Terms of Independent Properties T and ʋ 277 Relation of dh in Terms of Independent Properties T and P 281 Alternative Formulation of the Web using T and P as Independent Properties 287 5.4 Departure Functions 290 Enthalpy Departure Function 290 Entropy Departure Function 293 5.5 Joule-Thomson Expansion and Liquefaction 298 Joule-Thomson Expansion 298 Liquefaction 301 5.6 Summary 304 5.7 Problems 305 Conceptual Problems 305 Numerical Problems 307 CHAPTER 6 Phase Equilibria I: Problem Formulation 315 Learning Objectives 315 6.1 Introduction 315 The Phase Equilibria Problem 316 6.2 Pure Species Phase Equilibrium 318 Gibbs Energy as a Criterion for Chemical Equilibrium 318 Roles of Energy and Entropy in Phase Equilibria 321 The Relationship Between Saturation Pressure and Temperature: The Clapeyron Equation 327 Pure Component Vapor–Liquid Equilibrium: The Clausius–Clapeyron Equation 328 6.3 Thermodynamics of Mixtures 334 Introduction 334 Partial Molar Properties 335 The Gibbs–Duhem Equation 340 Summary of the Different Types of Thermodynamic Properties 342 Property Changes of Mixing 343 Determination of Partial Molar Properties 357 Relations Among Partial Molar Quantities 366 6.4 Multicomponent Phase Equilibria 367 The Chemical Potential—The Criteria for Chemical Equilibrium 367 Temperature and Pressure Dependence of μi 370 6.5 Summary 372 6.6 Problems 373 Conceptual Problems 373 Numerical Problems 377 CHAPTER 7 Phase Equilibria II: Fugacity 391 Learning Objectives 391 7.1 Introduction 391 7.2 The Fugacity 392 Definition of Fugacity 392 Criteria for Chemical Equilibria in Terms of Fugacity 395 7.3 Fugacity in the Vapor Phase 396 Fugacity and Fugacity Coefficient of Pure Gases 396 Fugacity and Fugacity Coefficient of Species i in a Gas Mixture 403 The Lewis Fugacity Rule 411 Property Changes of Mixing for Ideal Gases 412 7.4 Fugacity in the Liquid Phase 414 Reference States for the Liquid Phase 414 Thermodynamic Relations Between γi 422 Models for γi Using gE 428 Equation of State Approach to the Liquid Phase 449 7.5 Fugacity in the Solid Phase 449 Pure Solids 449 Solid Solutions 449 Interstitials and Vacancies in Crystals 450 7.6 Summary 450 7.7 Problems 452 Conceptual Problems 452 Numerical Problems 454 CHAPTER 8 Phase Equilibria III: Applications 466 Learning Objectives 466 8.1 Vapor–Liquid Equilibrium (VLE) 467 Raoult’s Law (Ideal Gas and Ideal Solution) 467 Nonideal Liquids 475 Azeotropes 484 Fitting Activity Coeffi cient Models with VLE Data 490 Solubility of Gases in Liquids 495 Vapor–Liquid Equilibrium Using the Equations of State Method 501 8.2 Liquid 1a2—Liquid 1b2 Equilibrium: LLE 511 8.3 Vapor–Liquid 1a2— Liquid 1b2 Equilibrium: VLLE 519 8.4 Solid–Liquid and Solid–Solid Equilibrium: SLE and SSE 523 Pure Solids 523 Solid Solutions 529 8.5 Colligative Properties 531 Boiling Point Elevation and Freezing Point Depression 531 Osmotic Pressure 535 8.6 Summary 538 8.7 Problems 540 Conceptual Problems 540 Numerical Problems 544 CHAPTER 9 Chemical Reaction Equilibria 562 Learning Objectives 562 9.1 Thermodynamics and Kinetics 563 9.2 Chemical Reaction and Gibbs Energy 565 9.3 Equilibrium for a Single Reaction 568 9.4 Calculation of K from Thermochemical Data 572 Calculation of K from Gibbs Energy of Formation 572 The Temperature Dependence of K 574 9.5 Relationship Between the Equilibrium Constant and the Concentrations of Reacting Species 579 The Equilibrium Constant for a Gas-Phase Reaction 579 The Equilibrium Constant for a Liquid-Phase (or Solid-Phase) Reaction 586 The Equilibrium Constant for a Heterogeneous Reaction 587 9.6 Equilibrium in Electrochemical Systems 589 Electrochemical Cells 590 Shorthand Notation 591 Electrochemical Reaction Equilibrium 592 Thermochemical Data: Half-Cell Potentials 594 Activity Coeffi cients in Electrochemical Systems 597 9.7 Multiple Reactions 599 Extent of Reaction and Equilibrium Constant for R Reactions 599 Gibbs Phase Rule for Chemically Reacting Systems and Independent Reactions 601 Solution of Multiple Reaction Equilibria by Minimization of Gibbs Energy 610 9.8 Reaction Equilibria of Point Defects in Crystalline Solids 612 Atomic Defects 613 Electronic Defects 616 Effect of Gas Partial Pressure on Defect Concentrations 619 9.9 Summary 624 9.10 Problems 626 Conceptual Problems 626 Numerical Problems 628