# Advanced Thermodynamics Engineering

## Book Preface

We have written this text for engineers who wish to grasp the engineering physics of thermodynamic concepts and apply the knowledge in their field of interest rather than merely digest the abstract generalized concepts and mathematical relations governing thermodynamics. While the fundamental concepts in any discipline are relatively invariant, the problems it faces keep changing. In many instances we have included physical explanations along with the mathematical relations and equations so that the principles can be relatively applied to real world problems.

The instructors have been teaching advanced thermodynamics for more than twelve years using various thermodynamic texts written by others. In writing this text, we acknowledge that debt and that to our students who asked questions that clarified each chapter that we wrote. This text uses a “down–to–earth” and, perhaps, unconventional approach in teaching advanced concepts in thermodynamics. It first presents the phenomenological approach to a problem and then delves into the details. Thereby, we have written the text in the form of a self–teaching tool for students and engineers, and with ample example problems. Readers will find the esoteric material to be condensed and, as engineers, we have stressed applications throughout the text. There are more than 110 figures and 150 engineering examples covering thirteen chapters.

Chapter 1 contains an elementary overview of undergraduate thermodynamics, mathematics and a brief look at the corpuscular aspects of thermodynamics. The overview of microscopic thermodynamics illustrates the physical principles governing the macroscopic behavior of substances that are the subject of classical thermodynamics. Fundamental concepts related to matter, phase (solid, liquid, and gas), pressure, saturation pressure, temperature, energy, entropy, component property in a mixture and stability are discussed.

Chapter 2 discusses the first law for closed and open systems and includes problems involving irreversible processes. The second law is illustrated in Chapter 3 rather than presenting an axiomatic approach. Entropy is introduced through a Carnot cycle using ideal gas as the medium, and the illustration that follows considers any reversible cycle operating with any medium. Entropy maximization and energy minimization principles are illustrated. Chapter 4 introduces the concept of availability with a simple engineering scheme that is followed by the most general treatment. Availability concepts are illustrated by scaling the performance of various components in a thermodynamic system (such as a power plant or air conditioner) and determining which component degrades faster or outperforms others. Differential forms of energy and mass conservation, and entropy and availability balance equations are presented in

Chapters 2 to 4 using the Gauss divergence theorem. The differential formulations allow the reader to determine where the maximum entropy generation or irreversibility occurs within a unit so as to pinpoint the major source of the irreversibility for an entire unit. Entropy generation and availability concepts are becoming more important to energy systems and conservation groups. This is a rapidly expanding field in our energy–conscious society. Therefore, a number of examples are included to illustrate applications to engineering systems. Chapter 5 contains a postulatory approach to thermodynamics. In case the reader is pressed for time, this chapter may be entirely skipped without loss of continuity of the subject.

Chapter 6 presents the state equation for real gases including two and three parameter, and generalized equations of state. The Kessler equation is then introduced and the methodology for determining Z (0) and Z (1) is discussed. Chapter 7 starts with Maxwell’s relations followed by the development of generalized thermodynamic relations. Illustrative examples are presented for developing tables of thermodynamic properties using the Real Gas equations.

Chapter 8 contains the theory of mixtures followed by a discussion of fugacity and activity. Following the methodology for estimating the properties of steam from state equations, a methodology is presented for estimating partial molal properties from mixture state equations.

Chapter 9 deals with phase equilibrium of multicomponent mixtures and vaporization and boiling. Applications to engineering problems are included. Chapter 10 discusses the regimes of stable and metastable states of fluids and where the criteria for stability are violated. Real gas state equations are used to identify the stable and unstable regimes and illustrative examples with physical explanation are given.

Chapter 11 deals with reactive mixtures dealing with complete combustion, flame temperatures and entropy generation in reactive systems. In Chapter 12 criteria for the direction of chemical reactions are developed, followed by a discussion of equilibrium calculations using the equilibrium constant for single and multi-phase systems, as well as the Gibbs minimization method. Chapter 13 presents an availability analysis of chemically reacting systems. Physical explanations for achieving the work equivalent to chemical availability in thermodynamic systems are included. The summary at the end of each chapter provides a brief review of the chapter for engineers in industry.

Exercise problems are placed at the end. This is followed by several tables containing thermodynamic properties and other useful information. The field of thermodynamics is vast and all subject areas cannot be covered in a single text. Readers who discover errors, conceptual conflicts, or have any comments, are encouraged to E–mail these to the authors (respectively, [email protected] and [email protected]).

The assistance of Ms. Charlotte Sims and Mr. Chun Choi in preparing portions of the manuscript is gratefully acknowledged. We wish to acknowledge helpful suggestions and critical comments from several students and faculty. We specially thank the following reviewers: Prof. Blasiak (Royal Inst. of Tech., Sweden), Prof. N. Chandra (Florida State), Prof. S. Gollahalli (Oklahoma), Prof. Hernandez (Guanajuato, Mexico), Prof. X. Li. (Waterloo), Prof. McQuay (BYU), Dr. Muyshondt. (Sandia National Laboratories), Prof. Ochterbech (Clemson), Dr. Peterson, (RPI), and Prof. Ramaprabhu (Anna University, Chennai, India).

KA gratefully acknowledges many interesting and stimulating discussions with Prof. Colaluca and the financial support extended by the Mechanical Engineering Department at Texas A&M University. IKP thanks several batches of students in his Advanced Thermodynamics class for proofreading the text and for their feedback and acknowledges the University of Illinois at Chicago as an excellent crucible for scientific inquiry and education.

Kalyan Annamalai, College Station, Texas

Ishwar K. Puri, Chicago, Illinois

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