Preface ....................................................... iii
Acknowledgments ................................................ xv
Authors ...................................................... xvii
Systems of Units .............................................. xix
Conversion Factors ............................................ xxi
1. Introduction ............................................... 1
Learning Objectives ........................................ 1
1.1 Definitions of Chemical Engineering ........................ 2
1.2 Sets of Units and Unit Conversion .......................... 3
1.2.1 Conversion of Units ................................. 3
1.2.2 Temperature Measurement ............................. 5
1.2.3 Temperature Conversion .............................. 6
1.3 Significant Figures ........................................ 8
1.3.1 Multiplication, Division, Addition, and Subtraction
of Significant Numbers .............................. 9
1.4 Dimensional Homogeneity ................................... 10
1.4.1 Dimensionless Quantities ........................... 11
1.5 Process and Process Variables ............................. 13
1.5.1 Process Flow Sheet ................................. 13
1.5.2 Process Unit ....................................... 13
1.5.3 Process Streams .................................... 13
1.5.4 Density, Mass, and Volume .......................... 13
1.5.5 Mass and Volumetric Flow Rates ..................... 14
1.5.6 Moles and Molecular Weight ......................... 16
1.6 Compositions of Streams ................................... 17
1.6.1 Mass Fraction and Mole Fraction .................... 17
1.6.2 Concentration ...................................... 19
1.7 Pressure Measurement ...................................... 22
1.7.1 Types of Pressures ................................. 23
1.7.2 Standard Temperature and Pressure .................. 24
1.7.3 Pressure-Sensing Devices ........................... 25
1.8 Process Classification and Material Balance ............... 38
1.8.1 Material and Energy Balances ....................... 38
Homework Problems ......................................... 39
References ................................................ 42
2. Process Units and Degrees of Freedom Analysis ............. 43
Learning Objectives ....................................... 43
2.1 Process Units: Basic Functions ............................ 44
2.1.1 Divider (Splitter) ................................. 44
2.1.2 Mixer (Blender) .................................... 44
2.1.3 Dryer (Direct Heating) ............................. 44
2.1.4 Filter ............................................. 45
2.1.5 Distillation Column ................................ 46
2.1.6 Multieffect Evaporator ............................. 46
2.1.7 Dehumidification ................................... 48
2.1.8 Humidifier ......................................... 48
2.1.9 Leaching and Extraction ............................ 49
2.1.10 Absorber (Stripper) ................................ 49
2.1.11 Partial Condenser and Flash Separator .............. 50
2.1.12 Flash Separator .................................... 50
2.1.13 Crystallizer ....................................... 51
2.1.14 Reactors ........................................... 51
2.1.15 Batch Reactor ...................................... 52
2.1.16 PFRs and PBRs ...................................... 53
2.1.17 CSTR and Fluidized Bed Reactor ..................... 53
2.2 Process Flow Diagram ...................................... 53
2.3 Labeling a PFD ....................................... 54
2.4 Degrees of Freedom Analysis .......................... 55
2.4.1 Possible Outcomes of DFA ...................... 56
2.5 Independent Equations ................................ 56
2.6 MultiunitPFD ......................................... 66
2.7 DFA, Multiunit Process ............................... 68
Homework Problems ......................................... 71
References ................................................ 74
3. Material Balance on Single-Unit Process ................... 75
Learning Objectives ....................................... 75
3.1 Introduction to Material Balance .......................... 75
3.2 Material Balance Fundamentals ............................. 77
3.3 Mass Balance on Steady-State Processes .................... 78
3.3.1 Stream Specification ............................... 78
3.4 Basis for Calculation ..................................... 83
3.4.1 Procedure for Solving Material Balance Problems .... 83
Homework Problems ........................................ 100
References ............................................... 102
4. Multiunit Process Calculations ........................... 105
Learning Objectives ...................................... 105
4.1 Multiunit Process ........................................ 105
4.2 Degrees of Freedom Analysis .............................. 106
4.3 Recycle, Bypass, Purge, and Makeup ....................... 108
4.3.1 Recycle ........................................... 108
4.3.2 Bypass ............................................ 109
4.3.3 Purge ............................................. 109
4.3.4 Makeup ............................................ 110
Homework Problems ........................................ 132
References ............................................... 135
5. Material Balances on Reactive Systems .................... 137
Learning Objectives ...................................... 137
5.1 Stoichiometry Basics ..................................... 138
5.1.1 Stoichiometric Equation ........................... 138
5.1.2 Stoichiometric Coefficients ....................... 138
5.1.3 Stoichiometric Ratio .............................. 138
5.1.4 Limiting Reactant ................................. 139
5.1.5 Excess Reactants .................................. 139
5.1.6 Fractional Conversion ............................. 143
5.2 General Material Balance ................................. 143
5.2.1 Differential Balance .............................. 144
5.2.2 Integral Balance .................................. 144
5.2.3 Formulation Approaches of Mass Balance ............ 145
5.3 Extent of Reaction Method for a Single Reaction .......... 145
5.4 Element or Atomic Balance Method ......................... 147
5.5 Molecular or Component Balance Approach .................. 147
5.6 Extent of Reaction and Multiple Reactions ................ 157
5.7 Molecular Species Approach for Multiple Reactions ........ 162
5.8 Degrees of Freedom Analysis for Reactive Processes ....... 168
5.8.1 Chemical Equilibrium .............................. 169
5.9 Combustion Reactions ..................................... 172
5.9.1 Theoretical and Excess Air ........................ 172
Homework Problems ........................................ 179
References ............................................... 182
6. Multiple-Unit Systems Involving Reaction, Recycle, and
Purge .................................................... 183
Learning Objectives ...................................... 183
6.1 Multiple-Unit Process Flowcharts ......................... 183
6.1.1 Flow Sheet for Reaction with Recycle .............. 184
6.1.2 Reaction with Product Splitter and Recycle ........ 184
6.1.3 Reaction with Recycle and Purge ................... 185
6.2 Degrees of Freedom Analysis for Reactive Multiple-Unit
Processes ................................................ 186
6.3 Reaction and Multiple-Unit Steady-State Processes ........ 192
Homework Problems ........................................ 208
References ............................................... 214
7. Single- and Multiphase Systems ........................... 215
7.1 Single-Phase Systems ..................................... 215
7.1.1 Liquid and Solid Densities ........................ 216
7.2 Ideal Gas Equation of State .............................. 217
7.2.1 Gas Density ....................................... 219
7.3 Real Gas Relationships ................................... 220
7.3.1 Compressibility Factor (z) ........................ 221
7.3.2 Virial Equation of State .......................... 222
7.3.3 van der Waals Equation of State ................... 222
7.3.4 Soave-Redlich-Kwong Equation of State ............. 223
7.3.5 Kay's Mixing Rules ................................ 225
7.4 Multiphase Systems ....................................... 228
7.4.1 Phase Diagram ..................................... 228
7.4.2 Vapor-Liquid Equilibrium Curve .................... 228
7.5 Vapor Pressure Estimation ................................ 229
7.5.1 Clapeyron Equation ................................ 230
7.5.2 Clausius-Clapeyron Equation ....................... 230
7.5.3 Cox Chart ......................................... 231
7.5.4 Antoine Equation .................................. 231
7.6 Partial Pressure ......................................... 234
7.6.1 Dalton's Law of Partial Pressures ................. 234
7.6.2 Raoult's Law for a Single Condensable Species ..... 235
7.7 Gibbs' Phase Rule ........................................ 241
7.8 Bubble Point, Dew Point, and Critical Point .............. 242
Homework Problems ........................................ 244
References ............................................... 246
8 Energy and Energy Balances ............................... 247
Learning Objectives ...................................... 247
8.1 Energy Balance for Closed and Open Systems ............... 247
8.1.1 Forms of Energy: The First Law of Thermodynamics .. 248
8.1.2 Energy Balance for a Closed System ................ 248
8.1.2.1 Kinetic Energy ................................ 249
8.1.2.2 Potential Energy .............................. 251
8.1.3 Energy Balance for an Open System ................. 253
8.1.4 Steam Turbine ..................................... 257
8.1.5 Heaters and Coolers ............................... 259
8.1.6 Compressors ....................................... 261
8.2 Mechanical Energy Balance ................................ 263
8.3 Bernoulli's Equation ..................................... 267
8.4 Enthalpy Calculations .................................... 268
8.4.1 Enthalpy Change as a Result of Temperature ........ 268
8.4.2 Constant Heat Capacity ............................ 271
8.5 Enthalpy Calculations with Phase Changes ................. 274
8.5.1 Energy Balance for Open Systems with Multiple
Inputs and Multiple Outputs ....................... 276
8.5.2 Enthalpy Change because of Mixing ................. 279
8.5.3 Energy Balance for Bioprocesses ................... 281
8.6 Psychrometric Chart ...................................... 283
8.7 Summary .................................................. 293
Homework Problems ........................................ 293
References ............................................... 297
9. Energy Balance with Reaction ............................. 299
Learning Objectives ...................................... 299
9.1 Heat of Reaction ......................................... 299
9.2 Heats of Formation and Heat of Combustion ................ 300
9.2.1 Extent of Reaction ................................ 304
9.2.2 Reactions in Closed Processes ..................... 304
9.3 Energy Balance for Reactive Processes .................... 307
9.3.1 Heat of Reaction Method ........................... 307
9.3.2 Heat of Formation or Element Balance Method ....... 308
9.4 Simultaneous Material and Energy Balances ................ 309
9.4.1 Unknown Process Exit Temperature .................. 322
9.5 Combustion Processes ..................................... 327
9.6 Energy Balance in Bioprocesses ........................... 332
9.7 Energy Balance in Membrane Reactors ...................... 334
9.8 Summary .................................................. 338
Homework Problems ........................................ 339
References ............................................... 342
10. Simultaneous Material and Energy Balances ................ 343
Learning Objectives ...................................... 343
10.1 Material Balances ........................................ 343
10.1.1 Conversion ........................................ 343
10.1.2 Yield ............................................. 344
10.1.3 Selectivity ....................................... 344
10.1.4 Extent of Reaction (Ј) ............................ 344
10.2 Energy Balances .......................................... 345
10.2.1 Heat of Reaction Method ........................... 345
10.2.2 Heat of Formation Method .......................... 345
10.2.3 Concept of Atomic Balances ........................ 346
10.2.4 Mathematical Formulation of the Atomic Balance .... 346
10.2.5 Degrees of Freedom Analysis for the Atomic
Balance ........................................... 346
10.2.6 Implementing Recycle on the Separation Process .... 349
Homework Problems ........................................ 375
References ............................................... 381
11 Unsteady-State Material and Energy Balances .............. 383
Learning Objectives ...................................... 383
11.1 Unsteady-State Material Balance .......................... 383
11.2 Unsteady-State Energy Balance ............................ 394
Homework Problems ........................................ 405
References ............................................... 406
Appendix ...................................................... 407
Index ......................................................... 437
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