Introductory Chemical Engineering - pearsoncmg.com

1 Introductory Chemical Engineering Thermodynamics, Second EditionThe Prentice Hall International Series in the Physical and Chemical Engineering Sciences had its auspicious beginning in 1956 under the direction of Neal R. Amundsen. The series comprises the most widely adopted college textbooks and supplements for Chemical Engineering education. Books in this series are written by the foremost educators and researchers in the field of Chemical a complete list of available sure to connect with us! Hall International Series in the Physical and Chemical Engineering SciencesIntroductory Chemical Engineering Thermodynamics, Second EditionJ. Richard ElliottCarl T. Lira Upper Saddle River, NJ Boston Indianapolis San Francisco New York Toronto Montreal London Munich Paris Madrid Capetown Sydney Tokyo Singapore Mexico CityMany of the designations used by manufacturers and sellers to distinguish their products are claimed as trademarks.

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4 First printing, February 2012vCONTENTSPREFACE xvii Notes to Studentsxviii AcknowledgmentsxviiiABOUT THE AUTHORSxixGLOSSARYxxiNOTATIONxxvUNIT I FIRST AND SECOND LAWS1 CHAPTER 1 BASIC CONCEPTS3 Introduction5 The Molecular Nature of Energy, Temperature, and Pressure6 Example The energy derived from intermolecular potentials12 Example Intermolecular potentials for mixtures14 The Molecular Nature of Entropy15 Basic Concepts15 Real Fluids and Tabulated Properties22 Example introduction to steam tables25 Example Interpolation27 Example Double interpolation27 Example Double interpolation using different tables28 Example Double interpolation using Excel29 Example Quality calculations31 Example Constant volume cooling32 Summary33 Practice Problems34vi Contents Homework Problems35 CHAPTER 2 THE ENERGY BALANCE39 Expansion/Contraction Work40 Shaft Work41 Work Associated with Flow41 Lost Work versus Reversibility42 Example Isothermal

5 Reversible compression of an ideal gas45 Heat Flow46 Path Properties and State Properties46 Example Work as a path function46 The Closed-System Energy Balance48 Example Internal energy and heat50 The Open-System, Steady-State Balance51 Example Pump work for compressing H2O55 The Complete Energy Balance56 Internal Energy, Enthalpy, and Heat Capacities57 Example Enthalpy change of an ideal gas: Integrating CPig(T)60 Example Enthalpy of compressed liquid60 Example Adiabatic compression of an ideal gas in a piston/cylinder61 Reference States63 Example Acetone enthalpy using various reference states65 Kinetic and Potential Energy66 Example Comparing changes in kinetic energy, potential energy, internal energy, and enthalpy66 Example Transformation of kinetic energy into enthalpy67 Energy Balances for Process Equipment68 Strategies for Solving Process Thermodynamics Problems74 Closed and Steady-State Open Systems75 Example Adiabatic, reversible expansion of an ideal gas75 Example Continuous adiabatic, reversible compression of an ideal gas76 Example Continuous, isothermal.

6 Reversible compression of an ideal gas78 Example Heat loss from a turbine79 Unsteady-State Open Systems80 Example Adiabatic expansion of an ideal gas from a leaky tank81 Example Adiabatically filling a tank with an ideal gas82 Example Adiabatic expansion of steam from a leaky tank83 Details of Terms in the Energy Balance85 Summary86 Practice Problems88 Homework Problems90 CHAPTER 3 ENERGY BALANCES FOR COMPOSITE SYSTEMS95 Heat Engines and Heat Pumps The Carnot Cycle96 Example Analyzing heat pumps for housing100 Distillation Columns101 Example Start-up for a distillation column103 introduction to Mixture Properties105 Ideal Gas Mixture Properties106 Contents vii Mixture Properties for Ideal Solutions106 Example Condensation of a vapor stream107 Energy Balance for Reacting Systems109 Example Stoichiometry and the reaction coordinate110 Example Using the reaction coordinates for simultaneous reactions111 Example Reactor energy balances116 Reactions in Biological Systems119 Summary121 Practice Problems122 Homework Problems122 CHAPTER 4 ENTROPY129 The Concept of Entropy130 The Microscopic View of Entropy132 Example Entropy change and lost work in a gas expansion137 Example Stirling s approximation in the Einstein solid141 The Macroscopic View of Entropy142 Example Adiabatic.

7 Reversible expansion of steam144 Example A Carnot cycle based on steam145 Example Ideal gas entropy changes in an adiabatic, reversible expansion149 Example Ideal gas entropy change: Integrating CPig(T)151 Example Entropy generation and lost work 151 Example Entropy generation in a temperature gradient152 The Entropy Balance153 Example Entropy balances for steady-state composite systems155 Internal Reversibility158 Entropy Balances for Process Equipment159 Example Entropy generation by quenching159 Example Entropy in a heat exchanger160 Example Isentropic expansion in a nozzle162 Turbine, Compressor, and Pump Efficiency164 Visualizing Energy and Entropy Changes165 Turbine Calculations166 Example Various cases of turbine outlet conditions168 Example Turbine efficiency calculation171 Example Turbine inlet calculation given efficiency and outlet172 Pumps and Compressors173 Example Isothermal reversible compression of steam173 Example Compression of R134a using P-H chart174 Strategies for Applying the Entropy Balance175 Optimum Work and Heat Transfer177 Example Minimum heat and work of purification180 The Irreversibility of Biological Life181 Unsteady-State Open Systems182 Example Entropy change in a leaky tank182 Example An ideal gas leaking through a turbine (unsteady state)

8 183 The Entropy Balance in Brief185 Summary185 Practice Problems187viii Contents Homework Problems189 CHAPTER 5 THERMODYNAMICS OF PROCESSES199 The Carnot Steam Cycle199 The Rankine Cycle200 Example Rankine cycle201 Rankine Modifications203 Example A Rankine cycle with reheat204 Example Regenerative Rankine cycle206 Refrigeration208 Example Refrigeration by vapor compression cycle209 Liquefaction212 Example Liquefaction of methane by the Linde process213 Engines214 Fluid Flow214 Problem-Solving Strategies214 Summary215 Practice Problems215 Homework Problems216 UNIT II GENERALIZED ANALYSIS OF FLUID PROPERTIES223 CHAPTER 6 CLASSICAL THERMODYNAMICS GENERALIZATIONS FOR ANY FLUID225 The Fundamental Property Relation226 Derivative Relations229 Example Pressure dependence of H233 Example Entropy change with respect to T at constant P234 Example Entropy as a function of T and P235 Example Entropy change for an ideal gas237 Example Entropy change for a simple nonideal gas237 Example Accounting for T and V impacts on energy238 Example The relation between Helmholtz energy and internal energy239 Example A quantum explanation of low T heat capacity240 Example Volumetric dependence of CV for ideal gas242 Example Application of the triple product relation243 Example Master equation for an ideal gas243 Example Relating CP to CV244 Advanced Topics244 Summary247 Practice

9 Problems248 Homework Problems248 CHAPTER 7 Engineering EQUATIONS OF STATE FOR PVT PROPERTIES251 Experimental Measurements252 Three-Parameter Corresponding States253 Generalized Compressibility Factor Charts256 Contents ixExample Application of the generalized charts258 The Virial Equation of State258 Example Application of the virial equation259 Cubic Equations of State260 Solving the Cubic Equation of State for Z263 Example Peng-Robinson solution by hand calculation266 Example The Peng-Robinson equation for molar volume266 Example Application of the Peng-Robinson equation268 Implications of Real Fluid Behavior269 Example Derivatives of the Peng-Robinson equation269 Matching the Critical Point270 Example Critical parameters for the van der Waals equation271 The Molecular Basis of Equations of State: Concepts and Notation271 Example Estimating molecular size273 Example Characterizing molecular interactions275 The Molecular Basis of Equations of State: Molecular Simulation276 Example Computing molecular collisions in 2D279 Example Equations of state from trends in molecular simulations281 The Molecular Basis of Equations of State.

10 Analytical Theories282 Example Deriving your own equation of state288 Summary289 Practice Problems290 Homework Problems291 CHAPTER 8 DEPARTURE FUNCTIONS301 The Departure Function Pathway302 Internal Energy Departure Function304 Example Internal energy departure from the van der Waals equation306 Entropy Departure Function307 Other Departure Functions308 Summary of Density-Dependent Formulas308 Pressure-Dependent Formulas309 Implementation of Departure Formulas310 Example Real entropy in a combustion engine310 Example Compression of methane using the virial equation312 Example Computing enthalpy and entropy departures from the Peng-Robinson equation314 Example Enthalpy departure for the Peng-Robinson equation316 Example Gibbs departure for the Peng-Robinson equation317 Example U and S departure for the Peng-Robinson equation317 Reference States318 Example Enthalpy and entropy from the Peng-Robinson equation320 Example Liquefaction revisited320 Example Adiabatically filling a tank