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### Elementary Principles of Chemical Process

Elementary Principles of Chemical Process

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Preface

An introductory stoichiometry course traditionally plays several important roles in the chemical engineering curriculum. On the most obvious level, it prepares the student to formulate and solve material and energy balances on chemical process systems and lays the foundation for subsequent courses in thermodynamics, unit operations and transport phenomena, kinetics and reactor design, and process dynamics and control. More fundamentally, it introduces the engineering approach to solving process-related problems: breaking a process down into its components, establishing the relations between known and unknown process variables, assembling the information needed to solve for the unknowns using a combination of experimentation, empiricism, and the application of natural laws, and, finally, putting the pieces together to obtain the desired problem solution.

We have tried in the book to fulfill each of these functions. Moreover, recognizing that the stoichiometry course is often the students' first real encounter with what they think may be their chosen profession, we have attempted to provide in the text a realistic, informative, and positive introduction to the practice of chemical engineering. In the first chapter we survey fields that recent chemical engineering graduates have entered, from traditional industrial chemistry and petroleum engineering to materials engineering, environmental science and technology, biomedical, biochemical, and genetic engineering, information technology, law, and medicine, and we describe the variety of research, design, and production problems engineers typically confront. In the rest of the book we systematically develop the structure of elementary process analysis: definitions, measurement, and calculation of process variables; conservation laws and thermodynamic relations that govern the performance of processes; and physical properties of process materials that must be determined in order to design a new process or analyze and improve an existing one.

The chemical process constitutes the structural and motivational framework for the presentation of all of the text material. When we bring in concepts from physical chemistry—for example, vapor pressure, solubility, and heat capacity—we introduce them as quantities whose values are required to determine process variables or to perform material and energy balance calculations on a process. When we discuss computational techniques such as curve-fitting, rootfinding methods, and numerical integration, we present them on the same need-to-know basis in the context of process analysis.

TOC

PART 1 ENGINEERING PROBLEM ANALYSIS 1

Chapter 1 What Some Chemical Engineers Do for a Living 3

Chapter 2 Introduction to Engineering Calculations 7

2.0 Instructional Objectives 7

2.1 Units and Dimensions 8

2.2 Conversion of Units 9

2.3 Systems of Units 10

2.4 Force and Weight 12

2.5 Numerical Calculation and Estimation 13

2.6 Dimensional Homogeneity and Dimensionless Quantities 20

2.7 Process Data Representation and Analysis 22

2.8 Summary 30

Problems 31

Chapter 3 Processes and Process Variables 42

3.0 Instructional Objectives 43

3.1 Mass and Volume 43

3.2 Flow Rate 45

3.3 Chemical Composition 47

3.4 Pressure 54

3.5 Temperature 60

3.6 Summary 63

Problems 65

PART 2 MATERIAL BALANCES 81

Chapter 4 Fundamentals of Material Balances 83

4.0 Instructional Objectives 83

4.1 Process Classification 84

4.2 Balances 85

4.3 Material Balance Calculations 89

4.4 Balances on Multiple-Unit Processes 104

4.5 Recycle and Bypass 110

4.6 Chemical Reaction Stoichiometry 116

4.7 Balances on Reactive Processes 125

4.8 Combustion Reactions 142

4.9 Some Additional Considerations about Chemical Processes

4.10 Summary 153

Problems 155

Chapter 5 Single-Phase Systems 187

5.0 Instructional Objectives 188

5.1 Liquid and Solid Densities 189

5.2 Ideal Gases 191

5.3 Equations of State for Nonideal Gases 199

5.4 The Compressibility Factor Equation of State 206

5.5 Summary 213

Problems 214

Chapter 6 Multiphase Systems 237

6.0 Instructional Objectives 239

6.1 Single-Component Phase Equilibrium 240

6.2 The Gibbs Phase Rule 247

6.3 Gas-Liquid Systems: One Condensable Component 249

6.4 Multicomponent Gas-Liquid Systems 255

6.5 Solutions of Solids in Liquids 264

6.6 Equilibrium Between Two Liquid Phases 271

6.7 Adsorption on Solid Surfaces 275

6.8 Summary 278

Problems 280

PART 3 ENERGY BALANCES 311

Chapter 7 Energy and Energy Balances 313

7.0 Instructional Objectives 314

7.1 Forms of Energy: The First Law of Thermodynamics 315

7.2 Kinetic and Potential Energy 317

7.3 Energy Balances on Closed Systems 318

7.4 Energy Balances on Open Systems at Steady State 320

7.5 Tables of Thermodynamic Data 325

7.6 Energy Balance Procedures 329

7.7 Mechanical Energy Balances 333

7.8 Summary 337

Problems 340

Chapter 8 Balances on Nonreactive Processes 357

8.0 Instructional Objectives 357

8.1 Elements of Energy Balance Calculations 358

8.2 Changes in Pressure at Constant Temperature 365

8.3 Changes in Temperature 366

8.4 Phase Change Operations 377

8.5 Mixing and Solution 395

8.6 Summary 406

Problems 409

Chapter 9

Balances on Reactive Processes 440

9.0 Instructional Objectives 441

9.1 Heats of Reaction 442

9.2 Measurement and Calculation of Heats of Reaction: Hess's Law 445

9.3 Formation Reactions and Heats of Formation 447

9.4 Heats of Combustion 448

9.5 Energy Balances on Reactive Processes 450

9.6 Fuels and Combustion 464

9.7 Summary 473

Problems 475

Chapter 9

Computer-Aided Balance Calculations 504

10.0 Instructional Objectives 504

10.1 Degree-of-Freedom Analysis Revisited 504

10.2 Sequential Modular Simulation 511

10.3 Equation-Based Simulation 522

10.4 Commercial Process Simulation Packages 533

10.5 Final Considerations 533

Problems 534

Chapter 10

Balances on Transient Processes 543

11.0 Instructional Objectives 543

11.1 The General Balance Equation ... Again 544

11.2 Material Balances 548

11.3 Energy Balances on Single-Phase Nonreactive Processes 554

11.4 Simultaneous Transient Balances 560

11.5 Summary 563

Problems 564

Chapter 12

Production of Chlorinated Polyvinyl Chloride 579

PVC Chlorination Reaction Chemistry 580

Process Description 581

Problems 584

Chapter 13

Steam Reforming of Natural Gas

and Subsequent Synthesis of Methanol 591

Process Description 592

Problems 595

Chapter 14

Scrubbing of Sulfur Dioxide from Power Plant Stack Gases 602

Process Description 603

Problems 605

Appendix A

Computational Techniques 607

A.l The Method of Least Squares 607

A.2 Iterative Solution of Nonlinear Algebraic Equations

A.3 Numerical Integration 622

Appendix B

Physical Property Tables 627

B.l Selected Physical Property Data 628

Heat Capacities 635

Vapor Pressure of Water 638

Antoine Equation Constants 640

Properties of Saturated Steam: Temperature Table 642

Properties of Saturated Steam: Pressure Table 644

Properties of Superheated Steam 650

Specific Enthalpies of Selected Gases: SI Units 652

Specific Enthalpies of Selected Gases: American Engineering Units

Atomic Heat Capacities for Kopp's Rule 653

Integral Heats of Solution and Mixing at 25°C 653

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