Preface 

xv  
Notation 

xix  
UNIT I FIRST AND SECOND LAWS 

1  (170) 


3  (32) 

The Molecular Nature Of Energy 


5  (5) 

Intermolecular potentials for mixtures 


10  (1) 

The Molecular Nature Of Entropy 


10  (1) 

Brief Summary Of Several Thermodynamic Quantities 


11  (4) 


15  (15) 

Introduction to steam tables 


22  (1) 


23  (1) 


24  (1) 

Double interpolation using different tables 


25  (1) 

Double interpolation using Excel 


26  (2) 


28  (1) 


29  (1) 


30  (1) 


31  (4) 


35  (52) 

Expansion/Contraction Work 


35  (1) 


36  (1) 

Work Associated With Flow 


37  (1) 

Lost Work VS. Reversibility 


38  (3) 

Isothermal compression of an ideal gas 


41  (1) 

Path Properties And State Properties 


41  (2) 


42  (1) 


43  (1) 

The ClosedSystem Energy Balance 


43  (4) 


45  (2) 

The OpenSystem, SteadyState Balance 


47  (2) 

The Complete Energy Balance 


49  (2) 

Internal Energy, Enthalpy, And Heat Capacities 


51  (7) 

Enthalpy of H2O above its saturation pressure 


53  (3) 

Adiabatic compression of an ideal gas in a piston/cylinder 


56  (1) 

Transformation of kinetic energy into enthalpy 


57  (1) 

Kinetic And Potential Energy 


58  (1) 

On the relative magnitude of kinetic, potential, internal energy and enthalpy changes 


58  (1) 

Energy Balances For Process Equipment 


59  (6) 

The integral representing shaft work 


64  (1) 

Strategies For Solving Process Thermodynamics Problems 


65  (1) 

Closed And SteadyState Open Systems 


66  (6) 

Adiabatic, reversible expansion of an ideal gas 


66  (2) 

Continuous adiabatic, reversible compression of an ideal gas 


68  (1) 

Continuous, isothermal, reversible compression of an ideal gas 


69  (1) 


70  (2) 

UnsteadyState Open Systems (Optional) 


72  (3) 

Adiabatic expansion of an ideal gas from a leaky tank 


72  (1) 

Adiabatically filling a tank with an ideal gas 


73  (1) 

Adiabatic expansion of steam from a leaky tank 


74  (1) 

Details Of Terms In The Energy Balance (Optional) 


75  (2) 


77  (1) 


77  (3) 


80  (7) 


87  (54) 


87  (2) 

Microscopic View Of Entropy 


89  (7) 

Entropy change vs. volume change 


93  (1) 

Entropy change of mixing ideal gases 


94  (2) 

The Macroscopic Definition Of Entropy 


96  (8) 

Ideal gas entropy changes in a piston/cylinder 


100  (2) 

Steam entropy changes in a piston/cylinder 


102  (1) 

Entropy generation in a temperature gradient 


102  (1) 

Entropy generation and lost work in a gas expansion 


103  (1) 


104  (6) 

Steadystate entropy generation 


105  (2) 

Reversible work between heat reservoirs, lost work 


107  (2) 

Entropy change of quenching 


109  (1) 


110  (2) 


112  (1) 


113  (1) 

Maximum/Minimum Work In Real Process Equipment 


114  (2) 

Entropy Balance For Process Equipment 


116  (1) 


117  (2) 


119  (2) 


120  (1) 


121  (1) 


122  (1) 

Strategies For Applying The Entropy Balance 


123  (1) 

Additional SteadyState Examples 


124  (3) 


124  (1) 

Entropy in a heat exchanger 


125  (2) 

UnsteadyState Open Systems (Optional) 


127  (2) 

Entropy change in a leaky tank 


127  (1) 

An ideal gas leaking through a turbine (unsteadystate) 


128  (1) 

The Entropy Balance In Brief 


129  (1) 


129  (1) 


130  (1) 


131  (10) 

Thermodynamics Of Processes 


141  (30) 


141  (2) 


143  (3) 


144  (1) 


145  (1) 


146  (3) 


146  (2) 

Regenerative Rankine cycle 


148  (1) 


149  (5) 

Refrigeration by vaporcompression cycle 


151  (3) 


154  (2) 

Liquefaction of methane by the Linde process 


155  (1) 

Internal Combustion Engines 


156  (5) 

Airstandard Brayton cycle thermal efficiency 


157  (1) 

Thermal efficiency of the Otto engine 


158  (2) 

Thermal efficiency of a Diesel engine 


160  (1) 


161  (3) 

ProblemSolving Strategies 


164  (1) 


165  (1) 


165  (6) 
UNIT II GENERALIZED ANALYSIS OF FLUID PROPERTIES 

171  (112) 

Classical ThermodynamicsGeneralization To Any Fluid 


173  (20) 

The Fundamental Property Relation 


174  (6) 


180  (6) 


176  (5) 

Entropy change with respect to T at constant P 


181  (1) 

Entropy as a function of T and P 


182  (1) 

Entropy change for an ideal gas 


183  (1) 

Entropy change for a simple nonideal gas 


183  (1) 

Application of the triple product relation 


184  (1) 


184  (1) 

Volumetric dependence of Cv for ideal gas 


185  (1) 

Master equation for an ideal gas 


185  (1) 


186  (1) 

Advanced Topics (Optional) 


186  (3) 


189  (1) 


190  (3) 

Engineering Equations Of State For PVT Properties 


193  (36) 

Experimental Measurements 


194  (1) 

ThreeParameter Corresponding States 


195  (3) 

Generalized Compressibility Factor Charts 


198  (2) 

Application of the generalized charts 


198  (2) 

The Virial Equation Of State 


200  (2) 

Application of the virial equation 


201  (1) 


202  (3) 

Solving The Equation Of State For Z 


205  (5) 

Solution of the PengRobinson equation for molar volume 


207  (1) 

Application of the PengRobinson equation 


208  (2) 

Implications Of Real Fluid Behavior 


210  (1) 

Derivatives of the PengRobinson equation 


210  (1) 

The Molecular Theory Behind Equations Of State 


210  (10) 

Deriving your own equation of state 


217  (3) 

Matching The Critical Point 


220  (1) 

Critical parameters for the van der Waals equation 


220  (1) 

Summary And Concluding Remarks 


220  (1) 


221  (1) 


222  (7) 


229  (28) 

The Departure Function Pathway 


230  (1) 

Internal Energy Departure Function 


231  (3) 

Entropy Departure Function 


234  (1) 

Other Departure Functions 


234  (1) 

Summary Of DensityDependent Formulas 


235  (6) 

Enthalpy and entropy departures from the PengRobinson equation 


236  (2) 

Real entropy in an engine 


238  (2) 

Enthalpy departure for the PengRobinson equation 


240  (1) 

Gibbs departure for the PengRobinson equation. 


241  (1) 

PressureDependent Formulas 


241  (2) 

Application of pressuredependent formulas in compression of methane 


242  (1) 


243  (4) 

Enthalpy and entropy from the PengRobinson equation 


245  (1) 


245  (2) 

Adiabatically filling a tank with propane (optional) 


247  (1) 

Generalized Charts For The Enthalpy Departure 


247  (1) 


247  (2) 


249  (1) 


250  (7) 

Phase Equilibrium In A Pure Fluid 


257  (26) 


258  (1) 

The ClausiusClapeyron Equation 


258  (2) 

ClausiusClapeyron equation near or below the boiling point 


260  (1) 

Shortcut Estimation Of Saturation Properties 


260  (4) 

Vapor pressure interpolation 


261  (1) 

Application of the shortcut vapor pressure equation 


262  (1) 

General application of the Clapeyron equation 


263  (1) 

Changes In Gibbs Energy With Pressure 


264  (2) 

Fugacity And Fugacity Coefficient 


266  (2) 

Fugacity Criteria For Phase Equilibria 


268  (1) 

Calculation Of Fugacity (Gases) 


268  (3) 

Calculation Of Fugacity (Liquids) 


271  (2) 

Calculation Of Fugacity (Solids) 


273  (1) 

Saturation Conditions From An Equation Of State 


274  (3) 

Vapor pressure from the PengRobinson equation 


274  (1) 

Acentric factor for the van der Waals equation 


275  (2) 


277  (1) 

Temperature Effects On G And f (Optional) 


278  (1) 


278  (1) 


279  (4) 
UNIT III FLUID PHASE EQUILIBRIA IN MIXTURES 

283  (198) 

Introduction To Multicomponent Systems 


285  (34) 


285  (3) 


288  (8) 


296  (5) 

VaporLiquid Equilibrium (VLE) Calculations 


301  (6) 

Bubble and dew temperatures and isothermal flash of ideal solutions 


305  (2) 


307  (3) 


310  (3) 

Advanced Topics (Optional) 


313  (1) 

Summary And Concluding Remarks 


314  (1) 


315  (1) 


315  (4) 

Phase Equilibria In Mixtures By An Equation Of State 


319  (36) 

The virial equation for vapor mixtures 


321  (1) 

A Simple Model For Mixing Rules 


321  (3) 

Fugacity And Chemical Potential From An EOS 


324  (5) 

Kvalues from the PengRobinson equation 


328  (1) 

Differentiation Of Mixing Rules 


329  (6) 

Fugacity coefficient from the virial equation 


331  (1) 

Fugacity coefficient for van der Waals equation 


332  (2) 

Fugacity coefficient from the PengRobinson equation 


334  (1) 

VLE Calculations By An Equation Of State 


335  (9) 

Bubble point pressure from the PengRobinson equation 


336  (1) 

Isothermal flash using the PengRobinson equation 


337  (2) 

Phase diagram for azeotropic methanol + benzene 


339  (1) 

Phase diagram for nitrogen + methane 


340  (2) 

Ethane + heptane phase envelopes 


342  (2) 

Strategies For Applying VLE Routines 


344  (1) 

Summary And Concluding Remarks 


345  (1) 


345  (1) 


346  (9) 


355  (68) 


356  (1) 

Modified Raoult's Law And Excess Gibbs Energy 


357  (6) 

Activity coefficients and the GibbsDuhem relation (optional) 


359  (1) 

VLE prediction using UNIFAC activity coefficients 


360  (3) 

Determination Of GE From Experimental Data 


363  (4) 

Gibbs excess energy for system 2propanol + water 


363  (2) 

Activity coefficients by the oneparameter Margules equation 


365  (1) 

VLE predictions from the Margules oneparameter equation 


365  (2) 

The Van Der Waals' Perspective 


367  (12) 

Application of the van Laar equation 


370  (1) 

Infinite dilution activity coefficients from van Laar theory 


371  (2) 

VLE predictions using regularsolution theory 


373  (2) 

ScatchardHildebrand versus van Laar theory for methanol + benzene 


375  (3) 

Combinatorial contribution to the activity coefficient 


378  (1) 


378  (1) 

FloryHuggins & Van Der Waals' Theories (Optional) 


379  (2) 


381  (19) 

Local compositions in a 2dimensional lattice 


383  (5) 

Application of Wilson's equation to VLE 


388  (9) 

Calculation of group mole fractions 


397  (1) 

Detailed calculations of activity coefficients via UNIFAC 


397  (3) 

Fitting Activity Models To Data (Optional) 


400  (3) 

Using Excel for fitting model parameters 


401  (2) 

T And P Dependence Of Gibbs Energy (Optional) 


403  (1) 

The Molecular Basis Of Solution Models (Optional) 


404  (6) 


410  (1) 


411  (1) 


412  (11) 

LiquidLiquid Phase Equilibria 


423  (22) 

The Onset Of LiquidLiquid Instability 


423  (1) 

Simple liquidliquidvapor equilibrium (LLVE) calculations 


424  (1) 

Stability And Excess Gibbs Energy 


424  (6) 

LLE predictions using FloryHuggins theory: polymer mixing 


426  (1) 

LLE predictions using UNIFAC 


427  (3) 

Plotting Ternary LLE Data 


430  (2) 

Vlle With Immiscible Components 


432  (1) 


432  (1) 

Critical Points In Binary Liquid Mixtures (Optional) 


433  (3) 

Liquidliquid critical point of the Margules oneparameter model 


434  (1) 

Liquidliquid critical point of the FloryHuggins model 


435  (1) 

Excel Procedure For Binary, Ternary LLE (Optional) 


436  (2) 


438  (1) 


439  (1) 


439  (6) 


445  (36) 


445  (14) 


459  (11) 

Eutectic behavior of chloronitrobenzenes 


463  (1) 

Eutectic behavior of benzene + phenol 


464  (1) 


465  (5) 


470  (5) 


475  (6) 
UNIT IV REACTING SYSTEMS 

481  (98) 


483  (46) 


483  (3) 

Stoichiometry and the reaction coordinate 


485  (1) 


486  (3) 

Calculation of standard state Gibbs energy of reaction 


487  (2) 

Reaction Equilibria For Ideal Solutions 


489  (3) 

Computing the reaction coordinate 


489  (1) 


490  (2) 


492  (2) 

Equilibrium constant as a function of temperature 


493  (1) 

Shortcut Estimation Of Temperature Effects 


494  (2) 

Application of the shortcut van't Hoff equation 


495  (1) 

Energy Balances For Reactions 


496  (6) 

Adiabatic reaction in an ammonia reactor 


498  (4) 

General Observations About Pressure Effects 


502  (1) 


503  (7) 

Simultaneous reactions that can be solved by hand 


503  (2) 

Solving multireaction equilibrium equations by EXCEL 


505  (2) 

Direct minimization of the Gibbs energy with EXCEL 


507  (2) 

Pressure effects for Gibbs energy minimization 


509  (1) 

Simultaneous Reaction And Phase Equilibrium 


510  (6) 

The solvent methanol process 


511  (3) 


514  (2) 

Electrolyte Thermodynamics 


516  (4) 

Chlorine + water electrolyte solutions 


517  (3) 

Solid components In Reactions 


520  (1) 

Thermal decomposition of methane 


521  (1) 

Summary And Concluding Remarks 


521  (1) 


522  (2) 


524  (5) 

Molecular Association And Solvation 


529  (50) 

Association And Solvation 


529  (5) 


534  (2) 


536  (1) 


537  (4) 

Compressibility factors in associating/solvating systems 


538  (1) 

Dimerization of carboxylic acids 


539  (1) 

Activity coefficients in a solvated system 


540  (1) 


541  (1) 

Pure Species With Linear Association 


542  (5) 

A Van Der Waals HBonding Model 


547  (8) 

Molecules of H2O in a 100ml beaker 


551  (4) 

The ESD Equation For Associating Fluids 


555  (10) 

Extension To Complex Mixtures 


565  (4) 

Statistical Associating Fluid Theory (SAFT) 


569  (2) 

Summary Analysis Of Association Models 


571  (2) 


573  (6) 
GLOSSARY 

579  (4) 
Appendix A SUMMARY OF COMPUTER PROGRAMS 

583  (16) 

A.1 HP48 Calculator Programs 


583  (4) 


587  (1) 

A.3 PC Programs For Pure Component Properties 


587  (1) 

A.4 PC Programs For Mixture Phase Equilibria 


587  (1) 


588  (1) 


589  (1) 

A.7 Downloading HP Programs 


589  (1) 

A.8 Using Fortran Programs 


589  (1) 

A.9 Notes On Excel Spreadsheets 


590  (5) 

A.10 Notes On HP Calculator 


595  (2) 


597  (2) 
Appendix B MATHEMATICS 

599  (14) 


599  (4) 

B.2 Solutions To Cubic Equations 


603  (3) 

B.3 The Dirac Delta Function 


606  (7) 

B.1 The Hard Sphere Equation of State 


608  (2) 

B.2 The SquareWell Equation of State 


610  (3) 
Appendix C STRATEGY FOR SOLVING VLE PROBLEMS 

613  (10) 


613  (5) 

C.2 Activity Coefficient (GammaPHI) Method 


618  (5) 
Appendix D MODELS FOR PROCESS SIMULATORS 

623  (8) 


623  (1) 


623  (1) 


624  (1) 


624  (1) 

D.5 Recommended Decision Tree 


625  (1) 

D.6 Thermal Properties Of Mixtures 


626  (2) 

D.1 Contamination from a reactor leak 


627  (1) 


628  (3) 
Appendix E PURE COMPONENT PROPERTIES 

631  (24) 

E.1 Ideal Gas Heat Capacities 


631  (3) 

E.2 Liquid Heat Capacities 


634  (1) 

E.3 Solid Heat Capacities 


634  (1) 


635  (1) 


636  (1) 

E.6 Enthalpies And Gibbs Energies Of Formation 


637  (3) 


640  (11) 

E.8 PressureEnthalpy Diagram For Methane 


651  (1) 

E.9 PressureEnthalpy Diagram For Propane 


652  (1) 

E.10 Thermodynamic Properties Of HFC134a 


653  (2) 
Index 

655  