Ba) Cora ers A Textbook of Crile mares le ITO TE Tes K.V. Narayanan[A Textbook of Chemical Engin by KV, Narayanan Ing Thermodynamics (© 2001 by PHI Learning Private Limited, New Dali, Al rights reserved. No part ofthis book ‘may be reproduced in any form, by mimeograph or any ether means, without permission in weting fom the publisher. 188N-970-01.200-1792-1 ‘The export rights of this book are vested solely with the publisher Fifteenth Printing : . a October, 2011 Published by Asoke K. Ghosh, PHI Leaning Private Limited, M-97, Connaught Circus, New Deth-110001 and Printed by Meenakshi Printers, Delh-1 10006.CONTENTS Preface x 1. INTRODUCTION AND BASIC CONCEPTS. 1-22 1.1 Scope and Limitations of Thermodynamics 1 1.2. Definitions and Fundamental Concepts 2 Systems and Processes 2 Homogeneous and Heterogenec Closed and Open Systems 3 State and Properties 3 Intensive and Extensive Properties 4 State and Path Funetions 4 . Pressure and Energy 5 Force 5 13.2 Pressure 5 13.3 Energy 6 1.4 Equilibrium State and the Phase 14.1 Steady State 10 1.4.2. Equilibrium Stare 10 1.4.3. Phase Rule 11 1.5. Temperature and Zeroth Law of Thermodynamics 11 15.1 Zeroth Law 11 15.2 Temperature 11 1.5.3 Ideal Gas Temperature Seale 12 1.6 Heat Reservoirs and Heat Engines 14 1.6.1 Heat Reservoir 14 1.6.2. Heat Engine 14 1.6.3. Heat Pump 15 1.7 Reversible and Irreversible Processes 16 Summary 20 Review Questions 20 Exercises 21 s Systems 3 10 FIRST LAW OF THERMODYNAMICS. 23-41 General Statements of First Law of Thermodynamics 23 ist Law of Thermodynamics for Cyclic Process 24 Internal Energy 24 First Law of Thermodynamies for Non-flow Process 2525° Enthalpy 28 2.6 First Law of Thermodynamics for Flow Process 30 2.7 Heat Capacity 34 Summary 38 Review Questions 38 Exercises 39 P-V-T BEHAVIOUR AND HEAT EFFECTS 42-78 3.1 P-V-T Behaviour of Pure Fluids 42 3.2 Equations of State and the Concept of Weal Gas 44 3.3. Processes involving Ideal Gases 45 3.3.1 Constant Volume Process 45 3.3.2 Constant Pressure Process 46 3.3.3 Constant Temperature Process 47 3.3.4 Adiabatic Process 48 3.3.5 Polytropic Process $0 3.4. Equations of State for Real Gases 53 3.4.1 Limiting Conditions $4 3.4.2 van der Waals Equation $4 3.4.3 Redlich-Kwong Equation 56 344 Redlich-Kwong-Soave Equation 57 345 Peng-Robinson Equation 57 3.46 Benedict-Webb-Rubin Equation 57 3.4.7 Virial Equation 58 35 Compressibility Charts 60 3.5.1 Principle of Corresponding States. 61 3.5.2 Generalised Compressibility Charts 62 3.6 Heat Effects accompanying Chemical Reactions 62 3.6.1 The Standard Heat of Reaction 62 3.6.2 The Standard Heat of Combustion 63 3.6.3. The Standard Heat of Formation 63 3.64 Hess's Law of Constant Heat Summation 64 3.6.5 Effect of Temperature on Standard Heat of Reaction 65 3.6.6 Temperature of Reaction 68 Summary 69 Review Questions 70 Exercises 71 SECOND LAW OF THERMODYNAMICS 79-114 4.1 Limitations of the First Law of Thermodynamics 79 4.1.1 Direction of Change 79 4.1.2 Qualitative Difference between Heat and Work 80 4.2 General Statements of the Second Law of Thermodynamics 80 4.2.1 The Equivalence of the Kelvin and Clausius Statements 81Contents Gy 43° Entropy 82 4.3.1 Why the Concept of Entropy? 82 43.2 Entropy and Heat 83 4.3.3. Enwopy and Temperature 84 4.3.4 Entropy and the Nature of the Process 84. 44° The Camot Principle 85 4.4.1 Thermodynamic Temperature Scale 87 4.4.2 Meal Gas as the Carnot Engine Working Substance 88 48 Entropy—A State Function 91 46 Caleulation of Entropy Changes 92 4.6.1 Phase Change 92 4.6.2 Processes involving Ideal Gases 93 4.6.3 Adiabatic Mixing Process 95 4.6.4 Isothermal Mixing of ideal Gases 96 4.6.5 Chemical Reactions 96 4.7 Clausius Inequality 97 4.8 Mathematical Statement of the Second Law of Thermodynamics 100 49° Entropy and Irreversibility 105 4.10 Statistical Explanation for Entropy 107 4.11 Third Law of Thermodynamics 108 Summary 109 Review Questions 110 Exercises 111 SOME APPLICATIONS OF THE LAWS OF THERMODYNAMI 5.1 Flow Processes 115 S.1.1 Continuity Equation 115 5.1.2 Energy Equation 116 5.1.3 Flow in Pipes 120 3.1.4 Flow through Nozzles 121 5.15 Ejectors 126 5.1.6 Throttling Process (Joule~Thomson Expansion) 127 5.1.7 Compressors 128 5.2 Refrigeration 135 Coefficient of Performance (COP) 135 Refrigerator Capacity 136 Camot Cycle 136 Vapour-compression Cycle 138 Choice of Refrigerant 143 Air-teftigeration Cycle 144 Absorption Refrigeration 147 Heat Pumps 148, 5.3 Liquefaction Processes 150 5.3.1 Vaporisation of Liquid 150 5.3.2 Free Expansion 150 5.3.3. Isentropic Expansion 152 115-18734 35 56 ‘The Steam-Power Plant 154 3.4.1 Rankine Cycle 154 3.4.2 Reheat Cycle 157 5.4.3. Regenerative Cycle 160 Internal Combustion Engines 163 5.5.1 Otto Cycle 164 5.5.2. Diesel Cycle 167 5.5.3 Dual Cycle 170 Gas-turbine Power Plant 171 5.6.1 Brayton Cycle 172 Summary 174 Review Questions 175 Exercises 176 ‘THERMODYNAMIC PROPERTIES OF PURE FLUIDS 188-253 61 62 63 6a 65 66 67 Classification of Thermodynamic Properties 188. 6.1.1 Relerence Properties 188 6.1.2 Energy Properties 188 6.1.3 Derived Properties 189 Work Function (Helmholtz Free Energy) 189 Gibbs Free Energy 190 Relationships among Thermodynamic Properties 191 6.4.1 Exact Differential Equations 191 6.4.2 Fundamental Property Relations 192 6.4.3 Maxwell's Equations 193 Clapeyron Equation 195 Enwopy-Heat Capacity Relationships 197 Differential Equations for Entropy 198 Modified Equations for U and H 199 Effect of Temperature, Pressure and Volume on U,H and $202 Relationship between Cp and Cy 207 Ratio of Heat Capacities 210 Effect of Pressure and Volume on Cp and Cy 210 JouleThomson Coefficient 214 Gibbs-Helmholtz Equation 216 Method of Jacobians 217 6.5.1 Properties of Jacobians 218 6.5.2 Thermodynamic Relations through the Method of Jacobians 219 Fugacity 225 ‘Standard State for Fugacity 226 Fugacity Coefficient 227 Effect of Temperature and Pressure on Fugacity 227 Determination of Fugacity of Pure Gases 228 Fugacities of Solids and Liquids 235, y 236 6.7.1 Effect of Pressure and Temperature on Activity 237Contents 6.8 Departure Functions and Generalised Charts 237 6.9 Thermodynamic Diagrams 240 6.9.1 Types of Diagrams 240 6.9.2 Consiruetion of Thermodynamic Diagrams 243 Summary 246 Review Questions 246 Exercises 248 PROPERTIES OF SOLUTIONS 254-308 7.1 Partial Molar Properties 254 7.1.1 Physical Meaning of Partial Molar Properties 255 7.1.2 Partial Molar Properties and Properties of Solution 257 7.1.3 Determination of Partial Molar Properties 260 7.2. Chemical Potential 265 7.2.1 Effect of Temperature and Pressure on Chemical Potential 266 7.3 Fugacity in Solutions 269 7.3.1 Fugacity in Gaseous Solutions 269 7.3.2 Lewis-Randall Rule 271 7.3.3 Fugacities in Liquid Solutions 272 7.3.4 Ideal Solutions and Raoult's Law 273 7.4 Henry's Law and Dilute Solutions 274 7.4.1 Ideal Behaviour of Real Solutions 274 7.4.2. Henry's Law and Gas Solubility 275 7.5. Activity in Solutions 277 75.1 Selection of Standard States 277 7.6 Activity Coefficients 278 7.6.1 Effect of Pressure on Activity Coefficients 280 7.6.2 Effect of Temperature on Activity Coefficients 280 7.7 Gibbs-Duhem Equations 283 7.8 Property Changes of Mixing 288 78.1 Activity and Property Change of Mixing 289 7.8.2 Property Changes of Mixing for Ideal Solutions 291 7.9 Heat Effects of Mixing Processes 292 7.10 Excess Properties 208 7.10.1 Excess Gibbs Free Energy 299 Summary 301 Review Questions 302 Exercises 303 PHASE EQUILIBRIA 309-397 8.1 Criteria of Phase Equilibrium 310 8.2 Criterion of Stability 312 8.3. Phase Equilibria in Single-component Systems 315 8.4 Phase Equilibria in Multicomponent Systems 318 8.5 Phase Rule for Non-reacting Systems 321 8.6 Duhem’s Theorem 3238.7 Vapour-Liquid Equilibria 324 8.8 Phase Diagrams for Binary Solutions 326 88.1 Constant-pressure Equilibria 326 8.8.2 Constant-temperature Equilibria 330 8.9 Vapour-Liguid Equilibria in Ideal Solutions 330 8.10 Non-ideal Solutions 340 8.10.1 Azeotropes 343 iquid Equilibria (VLE) at Low Pressures 347 BALI Activity Coefficient Equations 347 8.12 Vapour-Liquid Equilibria involving High Pressures and Multicomponent Systems 362 8.12.1 Vaporisation Equilibrium Constants 362 8.12.2 Bubble-poim Equilibria 362 8.12.3 Dew-point Equilibria 363 8.124 Flash Vaporisation 363, 8.13 Consistency Test for VLE Data 367 8.13.1 Using Slope of In y Curves 368 8.13.2 Using Data at the Mid-point 369 8.13.3 Redlich-Kister Method 369 8.134 Using the Coesistence Equation 371 8.13.5. Using the Partial Pressure Data 372 8.14 Caleulation of Activity Coefficients using Gibbs-Duhem Equation 373 8.15. VLE for Systems of Limited Miscibility 376 8.15.1 Partially Miscible Systems 376 8.15.2 Immiscible Systems 377 8.16 Liquid-Liquid Equilibvium Diagrams 381 8.16.1 Binary Liguid-Liquid Equilibria 381 8.16.2 Ternary Equilibrium Diagrams 382 Summary 383 Review Questions 384 Exercises 386 ICAL REACTION EQUILIBRIA 398-450 Reaction Stoichiometry 399 Criteria of Chemical Reaction Equilibrium 402 9.3 Equilibrium Constant 404 9.4 Equilibrium Constant and Standard Free Energy Change 406 9.4.1 Choice of Standard State 407 9.42 Feasibility of a Reaction 407 9.8 Effect of Temperature on Equilibrium Constant 409 9.5.1 Evaluation of Equilibrium Constants 413 9.5.2 Giaugue Functions 413 9.6 Effect of Pressure on Equilibrium 419 9.6.1 Effect of Pressure on Equilibrium Constant 419 9.6.2 Effect of Pressure on Equilibrium Composition 419Contents Lx] 9.7 Other Factors Affecting Equilibrium Conversion 422 9.7.1 Presence of Inert Materials 423 9.7.2 Presence of Excess of Reactants 426 9.7.3 Presence of Products 427 9.8 Liquid-phase Reactions 429 9.9 Heterogeneous Reaction Equilibria 431 9.9.1 Reactions in Solutions 431 9.9.2 Equilibria involving Pure Solids and Liquids 431 9.9.3 Pressures of Decomposition 432 9.10 Simultaneous Reactions 434 9.11 Phase Rule for Reacting Systems 437 Summary 439 Review Questions 440 Exercises 441 Appendixes 451-498, A. Table for Thermodynamic Properties of Saturated Steam 451 B, Table for Thermodynamic Properties of Superheated Steam 453 C. Aptitude Test in Chemical Engineering Thermodynamics 459 References 499-500 Answers to Exercises 501-508 Index 509-516PREFACE ‘The field of chemical engineering is conventionally classified into two broad categories: the unit ‘operations and the unit processes, The former involves physical transformation and the latter ‘chemical changes. The chemical engineer, whether he is concerned with the unit operations or with the unit processes has to evaluate the energy requirements for initiating these transformations, study the energy changes involved in such processes, and determine the extent to which these transformations can be carried out. The science of thermodynamics deals exactly with these problems and a strong foundation in thermodynamics is therefore a must for the success of chemical engineer in his professional life. Chemical engineering thermodynamics is one of the core courses in the undergraduate ‘chemical engineering curriculum, In this course, more emphasis is given to the treatment of properties of solutions, phase equilibria and chemical reaction equilibria, all coming under the realm of “chemical thermodynamics’ rather than on the thermodynamic analysis of heat engines and heat-power cycles. The conventional texthooks on thermodynamics are, therefore, inadequate to meet these requirements. Hence the need for a book on thermodynamics that deals exclusively with the theory and applications of chemical engineering thermodynamics. During the several years of my experience in teaching thermodynamics to the undergraduate students, I have come dcross students who have strong ‘likes’ and ‘dislikes’ toward the subject. Unfortunately, the latter frequently outnumber the former. The seemingly abstract nature of thermodynamic principles is only partly to blame for this scenario. The major reason is the dearth Of student-friendly textbooks that help the student in providing a sound basis and act as catalysts for going deeper into the subject. An unwilling student should not be compelled to studying the vast subject of thermodynamics, without giving him or her a proper orientation. These inadequacies Of the existing books on the subject have been kept in mind while writing this book. An earnest attempt has been made to eliminate avoidable rigour and intricacies that usually make the subject ‘dry. Instead, the book tries to provide a firm foundation in the theory through the application ‘of the fundamentals to solve practically important problems. This book is intended to serve as a texthook for the undergraduate students in chemical ‘engineering and other related branches of engineering such as polymer engineering, petroleum, engineering, and safety and environmental engineering. Numerical examples given under each section would help the student gain a better insight into the theory. In this text, only SI units used. Review questions at the end of the chapters would help the student check his/her understanding ‘of the topics discussed in each chapter before going to the next. Each chapter is provided with a number of exercise problems, and answers to all of them are given at the end of the book. A ‘number of objective-type questions are included in the Appendix: “An Aptitude Test in Chemical Engineering Thermodynamics’, The student would find these very helpful in preparing for competitive examinations. Most of the questions presented in this section are taken from earlier Graduate Aptitude Test in Engineering (GATE) question papers. This book is the outgrowth of the several lectures I have delivered to the chemical engineering students in the Government Engineering College, Thrissur. The response from the students who benefitted from these lectures was a major source of inspiration for writing this book. Valuable xoy Pretace help and suggestions at various stages in its evolution have contributed towards bringing it out in the present form. My colleagues at the Government Engineering Colleges at Thrissur and Calicut provided a helpful environment for undertaking this work and I am very grateful towards all of them, I recall with gratitude the stimulating experience I spent at IIT Madras during my research work under Prof. M.S. Ananth, which contributed much in sustaining my interest in the subject of thermodynamics. I am thankful to the Director of Technical Education, Kerala and the Government of Kerala for granting me permission to publish the book. And my special thanks are due to my wife Lakshmi for her suggestions for improving the quality and content of the book as also for the cooperation in accommodating the lengthy hours that I spent during the preparation of the manuscript. Thanks are also due to my daughter Aparna for her patience and understanding even when I could not attend to her due to my preoccupation in this book-writing project. Comments, constructive criticism and suggestions for improving the quality of the book would be gratefully accepted, KY. NARAYANANINTRODUCTION AND BASIC CONCEPTS ‘The science of thermodynamics deals with energy and its transformation, It tells us about the direction in which changes take place in nature. It also determines the conditions under which 4 proposed change attains a state of equilibrium—a state in which no further change is possible under the given conditions. Original thermodynamic formulae were applied to a limited class of processes such as those occurring in heat engines. Thermodynamic analysis is now applied to a ‘wide variety of problems covering both physical and biological sciences. Thermodynamics finds extensive applications in chemical engineering. The field of chemical engineering is commonly Alivided into two: tit operations and unit processes. The former involves only physical transformation such as gas absorption, distillation, heat transfer, and filtration, whereas the latter consists of the combination of the physical changes with chemical processes such as oxidation, nitration, and catalysis. In chemical processes, like the synthesis of ammonia from a mixture of nitrogen and hydrogen, thermodynamics enables us to determine the maximum yield of ammonia obtained under given conditions of temperature and pressure. In a unit operation like distillation, it predicts the minimum reflux ratio provided in the fractionation column (o achieve a spevilied separation. The fundamental problems that a chemical engineer encounters, whether they are related to unit operations or to unit processes, involve two basic aspects of a change—the equilibrium and the rate of change. The strength and limitations of thermodynamics will become ‘obvious when we try to find answers to these problems. 1.1 SCOPE AND LIMITATIONS OF THERMODYNAMICS The heat and work effects accompanying a physical or chemical process can be accurately predicted using thermodynamic calculations. What is the maximum work obtained from a. specified change in the state of the system? Or, what is the minimum work required to effect a certain change in the system? What is the efficieney with which work is produced when a fuel is burned in a steam engine? The answers to these questions are readily provided by thermodynamics, Thermodynamics sets certain limits to the various processes occurring in nature. It also helps us to determine a priori whether a proposed process is possible or not. Since it deals with the direction of change and equilibrium, it enables one to calculate the equilibrium conditions for both physical and chemical changes. For example, thermodynamics can predict the equilibrium yield in a chemical reaction and also gives insight into the driving force for the change under the given conditions of temperature and pressure, The equilibrium yield gives the engineer an ultimate value that he strives to attain by ying improvements in the process. Attempts to cross 1A Textbook of Chemical Engineering Thermodynamics these limits have all been futile as is evident from the history of the evolution of blast furnace technology for iron making. In the blast furnaces, iron is produced by reduction of iron oxide by carbon monoxide. FeO; + 3CO + 2Fe + 3COs In the early years of the development of blast furnace technology, the presence of carbon ‘monoxide in the effluent gases was thought to be due to insufficient contact time in the furnace. ‘To improve the time of contact of coal with the ore, furnaces as tall as 30 to 40 m were built, bbut the conversion could not be improved. The concept of equilibrium conversion was not recognised at that time. Later, with the application of thermodynamics to chemical reaction equilibrium, it became clear that in a chemical reaction conversions above the equilibrium value could never be attained in practice, Apart from predicting the equilibrium yield, thermodynamics also helps us to derive information on the possible side reactions and methods of eliminating undesired products. It can also help us in selecting the optimum conditions for the reaction such as the temperature, ‘Though thermodynamics can tell us whether a chemical reaction is possible or not, it cannot say whether a possible reaction will actually oceur of not. The rate of any process may be written as the ratio of the driving force to resistance. Thermodynamics ean tell us about the driving force, bout resistance to Flow of energy or material introduces questions of mechanisms that are outside its scope. Consequently, it cannot say at what rate the system approaches equilibrium. That is, thermodynamics cannot predict whether a specified change will take place in a reasonable period of time or not. As an example, consider the unit operation of gas absorption. The driving force for the absorption of a gas in aliquid, the energy requirements, the minimum amount of absorbing liquid required, etc., could be determined from thermodynamic considerations, But the rate of absorption is influenced by many other factors that are alien to thermodynamies. Thermodynami can predict the minimum work required in a process, but the actual work requirement can be determined only if we know the losses like friction that are unavoidable. Not withstanding these limitations, thermodynamics remains a powerful and universal tool ‘with the engineer. It enables us to calculate the maximum amount of work a given fuel can produce in a steam engine, the maximum efficiency of a turbine or a refrigerator and the maximum yield in a given chemical reaction. It also helps us in establishing the optimum range of ‘emperatures and pressures that are to be used in a chemical or physical process and it guides us in the choice of solvent to be used in such separation operations as gas absorption and liquid extraction. pressure, concentration of reactants, etc. 1.2 DEFINITIONS AND FUNDAMENTAL CONCEPTS. 1.2.1. Systems and Processes System. In thermodynamics, a substance or group of substances in which we have special interest is called a sysiem. It is that part of the universe which is set apart for our special consideration. It may be @ reaction vessel, a distillation column, or a heat engine, Process. ‘The changes taking place within the system is referred 10 as a process. Thus, hydrocarbon. fuel and oxygen in a combustion chamber constitute the system and the combustion of fuel to form water and carbon dioxide constitutes a process.Introduction and Basic Concepts Surroundings. The part of the universe outside the system and separated from the system by boundaries is called surroundings. The boundaries may be either physical or imaginary; they may be rigid or movable, For practical reasons, the surroundings are usually restricted to that portion of the universe which is in the immediate vicinity of the system and ave affected by changes ‘occurring in the system. For example, when the steam condensing in a shell-and-tube heat exchanger is treated as the system, the cooling water to which the latent heat of vaporisation is twansferred may be treated as the surroundings. 1.2.2 Homogeneous and Heterogeneous Systems Homogeneous system. This system is also called a phase, Here the properties are the same throughout or the properties vary smoothly without showing any surface of discontinuity. Liquid water in a beaker and a column of dust-free air above the earth's surface are examples of homogeneous system. Heterogeneous system. This is a system which consists of two or more distinet homogeneot regions or phases. There is a sudden change in properties at the phase boundaries. A liquid mixture of benzene and water forms a heterogeneous system made up of two immiscible liquid phases. Water and water vapour taken in a closed container is another example of a heterogeneous system. Systems consisting of only gases and vapours are always homogeneous. With Tiquids, two phases are common, and with solids any number of different phases are possible, 1.2.3 Closed and Open Systems Closed system and open system. Systems that can exchange energy with the surroundings ‘ut which cannot transfer matter across the boundaries are known as closed systems. Open systems, oon the other hand, can exchange both energy and matter with their environment, In a multiphase system, each phase is open since material is free to enter and leave each phase, although the system as a whole may be closed to the flow of matter. A batch reactor is a closed system while a tubular flow reactor is an open system. Cyclical processes, like power and refrigeration eyeles closed systems when considered as a whole, whereas each component of the cycle such as compressor, pump, and heat exchanger is open. Isolated system. This isa system, which is totally unaffected by the changes in its environment Neither energy nor matier ean eross the boundaries of an isolated system. A closed system is thermally isolated, when the enclosing walls are impervious to the flow of heat; it is mechanically isolated, when enclosed by rigid walls, and is completely isolated. when neither material nor energy in any form can be added to it or removed from it, A perfectly isolated system is an ideal concept that cannot be attained in practice. The system and surroundings considered together constitute an isolated system. Thus, the universe can be treated as an isolated system, 1.2.4 State and Properties Certain specifications such as pressure, volume, and temperature are necessary to define the conditions of a given system. The condition defined by such specifications is called the state ofA Textbook of Chemical Engineering Thermodynamics the system. The variables used to define the state are called the state functions or the properties of the system. The minimum number of such variables required to represent the state uniguely depend on the number of phases constituting the system and the number of distinct chemical species present in the system (see the phase rule). The properties generally used to represent the state of a homogeneous system consisting of a single substance are the pressure, the volume, and the temperature. However, any one of these three properties depends upon the other two. Thus, if two properties, say, pressure and the temperature are specified, all other physical properties, eg. density, viscosity, reftactive index are thereby definitely fixed. Thus, thermodynamic properties serve to define the state of a system completely, 1.2.5. Intensive and Exten: e Properties The extensive properties depend on the quantity (or extent) of matter specified in the system, Mass and volume are extensive properties. The total value of any extensive property is the sum of the values of the property of individual components into which the system ean be subdivided. An intensive property is independent of the size of the system, Pressur temperature, specific volume, density, etc., are intensive properties, Some intensive properties are derived from the extensive properties by specifying the unit amount of the substance concerned. Examples are specifie volume, specific heat, and density. Heat capacity is an extensive property, while specific heat is an intensive property. As the intensive properties are independent ‘of the amount of the substance, they describe specific characteristics of a substance in a given state, 1.2.6 State and Path Functions State functions. Properties of a substance deseribe its present state and do not give a record of its previous history. They are state functions in the sense that they are fixed for a particular state of the system and do not in any way depend upon the past history or the path by which the state was arrived at. When a system is considered in two different states, the difference in property between the two states depends solely upon those states themselves and not upon the manner in whieh the system changes from one state to the other. For example, AM, the change in some property M of the system as it changes from state 1 to state 2, is always the same regardless of the process by which the change is brought about. For a eyelic process, the initial and final states are the same and the change in the property AM will be zero, Path functions. The values of heat and work accompanying a given change in state vary with the path from the initial to the final state. For example, some mass of hydrocarbon may be completely burnt in air at constant volume in a combustion chamber. AM the energy lost by the system appears as heat, no work being done. In contrast, a large part of the energy of the hydrocarbon-air system is converted to mechanical work and only the remainder into heat in an internal combustion engine. It means that the heat and work involved in a given change of state are not to be determined solely by the initial and final states: they also depend on the manner in which the change is carried out, Heat and work are therefore not thermo- dynamic properties of the system. They are properties of the process and are called path Junctions.Introduction and Basic Concepts 1.3 FORCE, PRESSURE AND ENERGY 1.3.1 Force According to Newton's second law of motion, the force acting on a body is directly proportional to the time rate of change of momentum. For a body of constant mass, Newton's law reduces to where F is the force, m is the mass of the body, a is the acceleration, and ¢ is a proportionality constant. In the ST system, the constant c is unity and we have F=ma ap When a body of mass 1 kg is accelerated by 1 m/s?, the foree aeting on the body is 1 kg m/s*, which is designated as 1 newton or (IN), EXAMPLE 1.1 A man circling the earth in a spaceship weighed 300 N at a location where the local gravitational acceleration was 4.5 m/s, Calculate the mass of the man and his weight on the earth where the gravitational acceleration is 9.81 m/s? Solution Force is equal to the product of mass and acceleration, i.e ‘Therefore, ‘The weight on the earth is the force acting on the object on the earth. F = 66.67 x 981 = 654 N 1.3.2 Pressure Pressure is defined as the normal component of the force per unit aren exerted by the fluid on a real or imaginary boundary. The unit of pressure in the SI system is newton per square metre (N/m?), also called the pascal (Pa). A multiple of pascal, called the bar, is also used as a unit of pressure, Thar = 105 Pa = 10° Nim? ‘The pressure exerted by the atmosphere is called the armospheric pressure and it varies with location and elevation on the earth's surface. One standard atmospheric pressure abbreviated as ‘atm is used in all system of units as an empirical unit of pressure, Iti the average pressure exerted by the earth's atmosphere at sea level. Pressure is sometimes expressed in terms of the height of the column of mercury, which it will support at a temperature of 273 K in a standard gravitational field. At standard atmospheric pressure this height is 0.76 m (760 mm or 760 torr) with density fof mercury taken as 13.5951 x 10° kg/m’.A Textbook of Chemical Engineering Thermodynamics 1.01325 bar = 1.01325 x 10° Pa 760 mm He 1 standard atmosphere (atm| 01325 x 10° Nim: ENAMPLE 1.2 4 special manometer fluid has a specific gravity of 2.95 and is used to measure a pressure of 1.15 bar at a location where the barometric pressure is 760 mm Hg. What height will the manometer fluid indicate? Solution If his the height of the manometer fluid, the mass of the fluid is m= hips where p is the density of the liquid and A is th ‘The force exerted by the fluid is area of eross-section of the column of liquid. F = ma = hpag where g is the acceleration due to gravity. ‘The pressure exerted by the fluid is Fa hps This should be equal tothe difference in pressures between the two ends of the manometer (AP) when the manometer indieates a steady reading. AP = hpe (2) Here, AP = Py - Py = 1.15 bar = 1.15 x 108 Nim? 1.91325 x 10° Nim? 0.13675 x 105 Nim? 760 mmm Hig = 1.01525 ba 15 x 108 ~ 1.01325 x 105 0.13675 x 10° = hpg = h(2.95 x 10°) x 9.8067 013878510" grey 2 A727 Bs 105 «8067 1.3.3. Energy Work. Energy is expended in the form of work when a force acts through a distance, Thus, aW=F dz 3) where W is the work done, F is the force acting, and Z is the displacement. The unit of work in the SI system is N m (newton metre) or J Goule). Let us consider the expansion or compression work in a cylinder, an important quantity in engineering thermodynamics. Assume that a gas is confined in a cylinder and let the pressure ofIntroduction and Basic Concepts the gas be P and volume V. IF the surface area of the piston exposed 10 the gas is A, the force acting on the piston is FPA (a ‘The displacemer AV of the gas as of the piston in the direetion of the foree dZ is related to the change in volume wv ae (5) Substituting Eqs. (1.4) and (1.5) in Eq, (1.3), we get aw Pav 6) If the volume of the gas changes from the initial value V; to the final value V3. Eg. (1.6) may be readily integrated to get the work done on the face of the piston: wef re an ‘The pressure-volume history of the gas undergoing the change in state is illustrated on the P-V diagram of Fig. 1.1. The integral of the Eq. (1.7) is given by the area under the curve between. the limits V; and V,. The area, and hence the work done in the compression or expansion of the ‘gas depend on the shape of the PV curve, thus establishing that the work done in a process is a path function, vs Volume vs Fig. 1.1 Work of expansion on the P-V diagram. Heat. 1tis that quantity which is wansferred between bodies due to the difference in temperatures existing between them. In the early years of the development of the stience of thermodynamics,A Textbook of Chemical Engineering Thermodynamics this quantity was thought of as a substance called calorie, Heat is now recognised as a form of energy that cannot be stored as such within the system. Heat is manifest only during a change of state of the system: itis energy in transit, like work. Heat exchanged in a process depends on the way in which the process is carried out, as pointed out earlier. Therefore, just as work, heat isa path function. And like work, itis expressed in joules, Two other units used for heat are the calorie and the BTU (the British thermal unit) 1 calorie = 4.1868 J; 1 BTU = 055.04 Energy. It is a quantity that can be stored within the system and can be exchanged between the system and the surroundings. The exchange of energy occurs either as heat or as work, Heat and work are called energy in transit; they cannot be stored within the system. Energy possessed by the system due to its position above some arbitrary reference plane is referred to as its potential energy (PE). If mass m is at an elevation above the ground, the potential energy of the mass PE = mg: (8) where g is the acceleration due to gravity. The energy possessed by the body by virtue of its ‘motion is called its kinetic energy (KE). IF a body of mass m is moving at a velocity u, the kinetic energy of the body is, Log KE = Lime 19) 7 a9) As is obvious, the kinetic energy and potential energy are not thermodynamic properties of the {do not change with change in the temperature or pressure of the body. In contrast, sy, which a system possesses by virtue of the molecular configuration and motion is a thermodynamic property of the system. Internal energy will be discussed in detail in Chapter 2, The unit of energy in SI system is joule (J) 1J=1Nm=1kg mis? Power. It is defined as the time rate of doing work, Its unit in the SI system is J/s, commonly designated as W (watts). In engineering calculations, power is sometimes expressed as horsepower (hp). Hence, | hp = 745.7 W. EXAMPLE 1.3 The potential energy of a body of mass 10.0 kg is 1.5 kJ. What is the height Of the body from the ground? Ifa body of mass 10 kg is moving at a velocity of $0 m/s, what is its kinetic energy? Solution ‘The potential energy (PE) is given by Eq, (1.8). Dt ge. 15 x 10° = 10 x 9.8067 x : 15.3. Thus the elevation 2 = 15.3 m.Introduction and Basic Concepts Kinetic energy (KE) is given by Eq. (1.9). KE =m? = + x 10 x (50) = 12500 N m= 12.5 kd 1 2 EXAMPLE 14 A man whose weight is 600 N takes 2 min for climbing up a stairease. What is the power developed in him, if the staircase is made up of 20 stairs each 0.18 m in height? Solution Total vertical displacement = 20 x 0.18 = 3.6 m Work done = Force x Displacement = 600 x 3.6 = 2160 Nm (= 2160 J) Power developed = Work done/Time 2160 2x60 Ils 8 W) EXAMPLE 15 Nitrogen gas is confined in a cylinder and the pressure of the gas is maintained by a weight placed on the piston. The mass of the piston and the weight together is 50 ke. The acceleration due to gravity is 9.81 m/s? and the atmospheric pressure is 1.01325 bar. Assume frietionless piston, Determine: (a) The force exerted by the atmosphere, the piston, and the weight on the gas if the piston is 100 mm in diameter. () The pressure of the gas, (€) If the gas is allowed to expand pushing up the piston and the weight by 400 mm, what is the work done by the gas in J? (@ What is the change in the potential energy of the piston and the weight after the expansion in part (c)? Solution (a) Force exerted by the atmosphere = Pressure x Area Lots «108 #400109 795.805. N Force exerted by the piston and weigh mx g = 50 x 981 00.5. N ‘Total force acting on the gas = 795.805 + 490.5 = 1286.305 N 1286,305 (b) Pressure = Force/Area = "053 ___ (14) 00 x10" 6378 & 10° Nim? 6378 bar) (©) Work done = Force x Displacement = 1286.305 x (400 x 10°) = 514.5 J (@) Change in the potential energy, A(PE} 50 x 9.81 x (400 x 10° mgs 196.2 510 A Textbook of Chemical Engineering Thermodynamics EXAMPLE 1.6 A spherical balloon of diameter 0.5 m contains a gas at | bar and 300 K. The {gas is heated and the balloon is allowed to expand. The pressure inside the balloon is found to vary linearly with the diameter. What would be the work done by the gas when the pressure inside reaches 5 bar’? Solution Since the pressure varies linearly with the diameter of the balloon, PID sonstant where P is the pressure inside the balloon and D is the diameter. Since these are respectively, Lx 10° Nim? and 0.5 m initially, P/D = 2 x 10° or P = 2 x 10D. As the final pressure is 5 x 108 Nim?, the final diameter would be 5 x 10'/2 x 10° = 2.5 m, Work done = f pav= f ex 10" Dy & cr)" That is, *) & x 2x10) Ff * pi ap== 5 4 x 10° @2.5' - 0.54) = 30.6305 x 10° Nm = 30.6305 x 10° 1.4 EQUILIBRIUM STATE AND THE PHASE RULE 1.4.1 Steady State ‘The distinction between steady state and the equilibrium state must be clear at the outset. A system, which is interacting with the surroundings, is said to have attained a steady-state condition when the properties at a specified location in the system do not vary with time. Consider the walls of a furnace, the inside surfuce of which is exposed to hot combustion gases and the outside surface to the atmospheric air. Heat wansfer occurs from the inside of the furnace to the outside and the temperature at a specified location in the wall varies with time. When the wall has attained steady state with respect to heat transfer, the temperature at any given point remains constant and does not vary with time. However, the temperatures at different points in the wall would be different. It is obvious that a system in the steady state exchanges mass, heat, for work with the surroundings, even when exhibiting time invariance for the properties. 1.4.2 Equilibrium State A system is said to be in a state of equilibrium if the properties are uniform throughout and they do not vary with time, By properties we mean the properties on a macroscopic scale and do not exclude the probability of individual molecules having different values for the properties. A system is in thermal equilibrium, when no heat exchange occurs between various points within the system and the temperature is uniform throughout. In a system which is in mechanical equilibrium, the pressure is uniform. Even under the conditions of uniform temperature and pressure, transfer of mass may occur between the various phases constituting the system, or chemical reaction may occur between the various components present in the system. In a system,Introduction and Basic Concepts i which is in a state of thermodynamic equilibrium, in addition to the absence of heat and work exchange, there would be no mass transfer between the phases, no diffusion of mass within the phase, and no chemical reaction between the constituents. A state of equilibrium implies, therefore, a state at rest, Since all such changes are caused by driving forces of some kind, the state of equilibrium may also be treated as the one in which all forces are in exact balance, The state of equilibrium will be retained by the system after any small, but short mechanical disturbance in the external conditions. 1.4.3 Phase Rule ‘The concept of equilibrium is important in thermodynamies, because, properties have any real ‘meaning only in the equilibrium state. The state of an equilibrium system consisting of a pure fluid is uniquely determined by specifying any two intensive variables, as observed earlier. Thus, when we say that COs gas is contained in a vessel at a pressure of 2 bar and temperature of 300 K,, the intensive state of the system is completely determined. The number of independent variables necessary to define the state of equilibrium uniquely is known as the number of degrees of freedom. This number will he different for different equilibrium states. For example, for water and water vapour in thermodynamie equilibrium, only one independent variable needs 10 be specified to define the state uniquely, The number of degrees of freedom in this case is just one. That is, when we say that this system is at a pressure of one standard atmosphere, the temperature gets automatically specified as 373 K, the normal boiling point of water. Thus, the specification Of pressure determines the temperature and all other intensive thermodynamic properties of the system. In fact, there exists a definite relationship between the number of degrees of freedom (F), the number of distinct chemical species constituting the system (C) and the number of phases present at equilibrium (7). This is given by the Gibbs phase rule, ‘The phase rule will be discussed in detail in Chapters 8 and 9. 1.5 TEMPERATURE AND ZEROTH LAW OF THERMODYNAMICS 1.5.1 Zeroth Law Let a body A be brought in thermal contact with another body B. Heat flows from one to the other and eventually thermal equilibrium is established between A and B. If another body C is also in thermal equilibrium with B, then it is experimentally observed that A and Care also in thermal ‘equilibrium, This observation although appears as frivolous, cannot be explained using known, scientific principles. Hence, it has come to be accepted as a law of nature. I is known as the zeroth Jaw of thermodynamics, as it precedes the first and second laws in the logical hierarchy of thermodynamic principles. It may be stated thus: Jf body A is in thermal equilibrium with B and B is in thermal equilibrium with C, then € is also in thermal equilibrium with A 1.5.2. Temperature ‘The temperature measures the degree of hotness oF coldness of a body. Since the physiological sensation of hotness or coldness does not give a quantitative measure of the temperature, we2 A Textbook of Chemical Engineering Thermodynamics should device some methods for defining and measuring it, The zeroth law of thermodynamics forms the basis for the measurement of temperature. When «wo bodies are in thermal equilibrium, ‘we say that the temperatures of both the bodies are equal. The zeroth law allows us to build thermometers which are devices that indicate the change in temperatures by the changes in some physical properties of the thermometer fluid, Such properties are called the thermometric properties. Commonly used thermometric properties include: Volume of gases and liquids (thermometers) Pressure of gases at constant volume (constant-volume gas thermometers) Electrical resistance of solids (thermistors) Electromotive forces of 1wo dissimilar metals (thermocouples) Intensity of radiation (pyrometers) Suppose the body B in the previous illustration is a glass capillary filled with mercury, which Wwe may call a thermometer. When it is in thermal equilibrium with body A, in height for the mercury column in the capillary that depends on the temperature of A. Ifthe thermometer, ‘when brought in contact with body C, indicates the same height for the column of mereury, we say that the bodies A and C are at the same temperature. To assign numerical values 10 the temperature, there should be some reference states, the temperatures of which are known, The reference states chosen are the ice point and the normal boiling point of water. In the Celsius scale of temperature, these reference states are arbitrarily assigned values 0°C and 100°C, respectively. ‘The interval between these two reference points is divided into 100 equal parts and each part is designated as one degree Celsius Tn the above method of temperature measurement, we have utilised the relative expansion of the glass and mercury, with temperature as the thermometric property. The variation of the thermometric property used for temperature measurement should be linear with temperature; otherwise, different thermometers will indicate same readings only at the fixed points. To circumvent this difficulty, a temperature scale that does not depend on the nature of the thermometrie uid is desired. The ideal gas thermometer provides, in a sense, such an absolute temperature seale, ithas a cer 1.5.3, Ideal Gas Temperature Scale A detailed discussion of ideal gas is given in Chapter 3. Here it suffices to treat an ideal gas as fone in which the distance between the molecules is $0 large that the inter-molecular forces are negligible and the volume occupied by the molecules is only a negligible fraction of the total volume, It follows from kinetic theory that for such a fluid the product of pressure and volume varies Tinearly with temperature, This is stated mathematically by the ideal gas eq) PV = RT, where R is a constant known as the ideal gas constant and V is the molar volume of the gas. All real gases behave ideally as pressure is reduced to zero. Thus, regardless of the nature of gas, the PV product approaches the same value at a given temperature for all gases, as P tends to zero. Thus, the quantity PV can be used as a thermometrie property to measure the temperature, regardless of the nature of the substance. Suppose, a low-pressure gas is confined in a constant volume gas thermometer as shown in Fig. 1.2. It is brought into contact with the system whose temperature is to be measured, By raising or lowering the tube containing mercury, the volume of the gas in the bulb can be maintained constant at the level M indicated in the FigureIntroduction and Basic Concepts we eal gas Fig. 1.2 Constant-volume gas thermometer The height h of the mercury column indicates the pressure P of the gas. Ifthe thermometer is now brought into contact with a system at the reference state, and the pressure P” measured, then Tw. 7 (Pye Since the volume is maintained constant, this equation leads to £ rR ‘The reference temperature chosen is the triple point of water, ie. the temperature at which the solid, liquid, and vapour phases of water coexist in equilibrium and it is assigned a value of 273.16 K. Hete, K is the abbreviation for degree Kelvin, the perature. Thus, by bringing the thermometer in contact with the system and by measuring the pressure P of the gas, the temperature T is given by unit for te P P rer Ler S > Pe where P°is the pressure indicated by the thermometer in equilibrium with the triple state of water. ‘The temperature scale based on this principle is relerted to asthe ideal gas temperature scale, The temperature indicated by this scale is found to be identical to the absolute thermodynamica A Textbook of Chemical Engineering Thermodynamics temperature that follows from the second law of thermodynamics which will be discussed in Chapter 4, Hence, the ideal-gas temperature has been accepted as an absolute temperature. ‘The triple-point temperature of water is found to be 0. 01 K higher than the ice point of water, the latter in Celsius scale being O°C. Thus, to convert the temperature measured in °C to the absolute temperature in K, we use’ T(K) = 100) + 273.15 where T is in K and r is in °C. In the FPS system of units the Fahrenheit seale is used to measure temperature, On this seule, the ice point is assigned a temperature 32°F and the normal boiling point of water a temperature 212°F. The interval between these wo fixed points is divided into 180 equal parts, each part indicating one degree Fahrenheit. The relationship between the temperature in degree Celsius and degree Fahrenheit is: TCR) = 1.84 (°C) +32 The absolute seale that corresponds to the Fahrenheit scale is called the Rankine scale. The c Fahrenheit (t) is related to the temperature in degree Rankine (7) as: T(R) = 1(CF) + 459.67 ‘The Rankine so Je is related to the Kelvin scale by TiR)= 8T(K) 1.6 HEAT RESERVOIRS AND HEAT ENGINES 1.6.1 Heat Reservoir A thermal reservoir is a sufficiently large system in stable equilibrium from which finite amount fof heat can be transferred without any change in its temperature. A heat source is a high temperature reservoir (HTR) from which heat is transferred and heat sink is a low temperature reservoir (LTR) t0 which heat is transferred. 1.6.2 Heat Engine ‘A heat engine is a thermodynamic system operating in a cycle to which heat is transferred and from which work is extracted. The thermal efficiency of a heat engine is defined as the ratio of ‘work output to the heat input. Figure 1.3 shows an engine that receives heat Q,, delivers work W and rejects heat Qs 10 the sink. The thermal efficiency (7) of the engine is defined as the ratio of work output (W) to the heat supplied (Q)) 7 a0)Introduction and Basic Concepts 6 High-temperature reservoir a * Engine w @ Low-temperature reservoir Fig. 1.3. Schematic representation of a heat engine. 1.6.3 Heat Pump A heat pump is a thermodynamic system operating in a cycle that removes heat from a low temperature body and delivers it to a high temperature ody. External energy in the form of work is necessary to accomplish this. Figure 1.4 shows a heat pump which receives heat Q2 from the sink and delivers heat Qj t the high temperature reservoir utilising external work W. The High-temperature reservoir % Pump w Low-temperature reservoir Fig. 1.4 Schematic representation of a heat pump. coefficient of performance (COP) of heat pump is defined depending upon the primary purpose for which itis used. When used as a refrigerator, the primary purpose is the removal of heat from fa low temperature system. The COP of a refrigerator is the ratio of heat transferred from low temperature reservoir (G3) to the work-input (W). For refrigerator, au When the heat output by the pump is our primary concern, the COP is defined as the ratio of heat rejected (Q,) 0 the work-input (W), For heat pu a =y a.6 A Textbook of Chemical Engineering Thermodynamics 1.7 REVERSIBLE AND IRREVERSIBLE PROCESSES Processes occur when there exists a driving force for a change of state between the parts of the system or between the system and the surroundings, If this driving force is finite, the process is irreversible and if itis infinitesimal in magnitude, the process is reversible. All spontaneous processes occurring in nature are irreversible, They cannot be reversed ‘without the use of external energy. IF the system undergoing an irreversible process were to be Drought back to its initial state, the surroundings would have to undergo some change through heat or work interactions. In short, as a result of the processes in the forward and reverse directions, if changes remain in the surroundings or in the system itself, the process would be irreversible, The free expansion of a gas is a highly irreversible process. When a gas at a high pressure is expanded by passing through a valve, it undergoes an irreversible change, because it cannot be compressed back to the original pressure without resort to energy from an external source like, say, a compressor. The natural processes like diffusion of a solute from a concentrated solution to a dilute one, the transfer of heat from a hot body to a cold body, rusting of iron in the presence of atmospheric oxygen, mixing of two pure gases, are all irreversible. Tn contrast, the direction of a reversible process ean be changed by an infinitesimal change in the forces acting on the system. A system undergoing a reversible process can he brought back to its original state, leaving no change in the surroundings. Consider water and water vapour in equilibrium contained in a eytinder provided with a frictionless piston, The external foree on the piston is kept equal to the force due to the vapour pressure of water at the given temperature, By increasing the force acting on the piston by an infinitesimally small amount, the vapour will condense; and decreasing it slightly will make water to vaporise. The process is very close to a reversible process as the work required to condense a certain amount of water vapour would be equal to that required to vaporise the same quantity of water, AAs another example of a reversible process consider the chemical reaction occurring in a galvanic cell in which the electrodes made of zine and platinum are immersed in an aqueous: solution of hydrochloric acid, The following reaction oceurs Zn + HCL > ZnCl, +H ‘The electrodes are connected through an external circuit to 4 potentiometer. The system is in equilibrium when the applied potential difference is balanced by the e.m.f, produced by the cell. By increasing or decreasing the potential difference slightly. the reaction can be carried out in the forward or reverse direction. Similarly, heat transfer between two bodies may be ma reversible by bringing down the temperature difference between them to a very small We see that in a reversible process the driving and opposing forces are in exact balance so that by increasing or decreasing the forces by an infinitesimal amount, the pracess ean be made to reverse the direction. Since the driving force differs from the opposing force by not more than a differential amount, it takes an infinite time for a reversible process to go to completion. Since ‘we engineers would like to carry out the processes in a Finite time, reversible processes are never attained in practice. Although such processes never occur in nature, they may be regarded as the limit of realisable processes. If all naturally occurring processes are irreversible, then why should we introduce the concept of reversible processes? The answer to this question can be provided by considering a simple example. A gas at high pressure is confined in a piston-eylinder arrangement. The piston is held in position by placing a suitable weight W over it. The pressure of the gas is balanced by theIntroduction and Basic Concepts 7 atmospheric pressure and the weight of the piston that includes the weight placed on it, Assume that the piston and cylinder neither absorb nor transmit heat and that the piston moves ‘within the cylinder without friction. Now, suppose that the mass W is removed by sliding it into a compartment on the side, Due to the force imbalance, the piston rises up as indicated in Fig. 15 " [»] Fig. 1.5. Iiveversible expansion of a gas. ‘The work done by the gas on expansion against the atmosphere is not available for restoring the {288 10 its initial state. If the gas returns to its original state, work would be done on the system, in which case, the surroundings undergoes some change. Therefore, the process is clearly an irreversible one, On the other hand, if the weight is raised to a higher level due to the expansion Of the gas, the potential energy of the surroundings would inerease and by utilising the increment in the potential energy, the state of the system can be restored. But, this is not happening her Decause the weight removed from the piston is at the same level as it was before the expansion ‘of the gas. It can be easily shown that the work appearing in the surroundings by the irreversible expansion of the gas cannot be measured as wef ra ‘The work of expansion done by the gas against the atmosphere is measured as the product of the force and the displacement of the piston. If F is the force acting downwards and dz is the displacement ofthe piso, then the work done against the atmoxpere in w = fF ds. When the fee sting downwards nd he ga pene at next halins,F = PA, hee A i the te J pay. ts AV is the increase in volume due to expansion. Once the weight W is removed from the piston, ofthe piston andthe work done by te gas agai the mosphere is PAde8 A Textbook of Chemical Engineering Thermodynamics the forces are out of balance: that is, the force exerted by the gas and the downward force are not equal. In this case, itis incorrect, if the work appearing in the surtoundings is evaluated as J Pav. wis oly for a eerste process, the Fores ar lay in exe lance and th work done by th aystan i evaluated fom te popes ofthe astm. Thus W = f PaV te applicable ony fora reversible proces. The eaeuation of work apearng inthe srtoundings ising the popes of the sytem i possible oly Hf he process eves The above proces canbe cared out reves ifthe weigh on ie piston 1 replaced by intiniely large mmber of fine pails together weighing W- Refer Pig 1. he prices were removed one aa ie, ie presore af the gas would never be out of balince with be downward frees. When fe ene weighs rmoved fom the piso, the pte energy af the urounings a _ fal i Fig. 1.8 Simulation of reversible expansion of a gas. is increased, as is evident from the height of the pile obtained on the side. The system does ‘maximum useful work on the surroundings. The weights can be replaced one by one on the piston and the piston can be made to retrace its path without using any extra energy from the surroundings. This is a reversible process, as the process can he reversed at any instant by an infinitesimally small increase in the downward forces and the original state of the system is restored without any change in the surroundings. The work done by the gas during expansion can be caleulated from the properties of the gas as [ P dV . It may also be noted that the reversible work is the m: ‘work obtainable if the process is expansion of the gas and the minimum work required if the process is compression. In the above process, we have assumed a frictionless piston, Though friction between the walls of the cylinder and the piston can be reduced in practice, it can never be completely eliminated. In the presence of friction, the work done by the gas in expanding from a high pressure to a lower value will be greater than the work appearing in the surroundings by the amount needed to overcome the effect of friction, In a similar manner, more work would have to be done by the surroundings to restore the system to the original state than that resulted from the forward process. It means that the presence of friction, however small it may be, eliminates the chances of achieving a reversible process in actual practice. Friction is not the only factor that causes irreversibility. Processes involving dissipative effects such as fluid flow, convectiveIntroduction and Basic Concepts 8 heat transfer, etc., can never be carried out reversibly. Reversible process is an idealised concept introduced in thermodynamics to compare the performance of actual processes. It represents limiting ease that can be approached, but never attained. In conclusion, we may summarise the characteristics of a reversible process as follows: 1. Ina reversible process, the driving and opposing forces are in exact balance, and an infinitesimal change in the extemal conditions would cause a reversal in the direction of the process 2, For reversible process to occur, friction, turbulence, and other dissipative effects should be absent 3, It takes an infinite time for its completion, 4. A reversible process occurring in a work-producing machine delivers the maximum amount of work and that occurring in a work-tequiring machine requires the minimum amount of work. 5, A reversible process is an idealised and imaginary concept and may be used for the comparison of the performance of actual systems and for indicating the efficiency of processes, EXAMPLE 1.7. Two kilograms of CO, gas is contained in a piston-cylinder assembly at a pressure of 6.5 bar and a temperature of 300 K. The piston has a mass of 5000 kg and a surface area of 1 m?, The frietion of the piston on the walls is significant and cannot be ignored. The atmospheric pressure is 1.01325 bar. The latch holding the piston in position is suddenly removed and the gas is allowed to expand. The expansion is arrested when the volume is double the original volume. Determine the work appearing in the surroundings. Will it be the same as the work done by the gas? Solution The initial volume of the ‘gas equation, PV = nkT. is evaluated assuming that the gas follows the ideal Number of moles of the gas nm = Mass/Molecular Weight = 2/44 = 0.0455 kmol 0.0455 (8.314 x 10°) x 300/6.5 x 10 V = 0.3492 m? Initial volume, V = n TIP 0.1746 m? Final volume = Change in the volume, AV = 2V ~ V = 0.1746 m* Pressure on the surroundings = Atmospheric pressure + Pressure due to the weight of the piston (01325 x 10° + 5000 x 9.8067 50359 x 108 Nim? Work done on the surroundings = PAV = (1.50359 x 10°) x 0.1746 = 0.2625 x 10° J Since the pressure of the gas is changing continuously, the work done by the gas cannot be evaluated as {P dV. This work woud be greder han the wor appsring nthe surroundings Because ofthe ieversible nature ofthe proces20 A Textbook of Chemical Engineering Thermodynamics SUMMARY ‘Thermodynamics deals with energy and its transformation, The heat and work effects accompanying fa process can he accurately predicted by thermodynamics. It imposes certain restrictions to all naturally occurring processes. The limits set by thermodynamics, such as the equilibrium yield in a chemical reaction, are the best that can be attained in a given situation. An important limitation of thermodynamies is its inability to predict the mechanisms of changes and hence, the rate of the process. An attempt is made in this chapter to introduce eertain basie concepts that are frequently employed in any thermodynamic analysis. The classification oF systems as closed aand open is based on whether matter can be exchanged between the system and the surroundings for not. The properties are classified as intensive and extensive on the basis of their dependence fon the quantity of matter involved. Thermodynamic quantities are classified as path functions and state functions, based on whether they are dependent on the past history of the system or not Heat and work were defined and were shown as examples of path functions. The SI units used for measuring some other thermodynamic quantities such as force, energy, temperature, and pressure were also given along with their definitions, The prineiple of measurement of temperature is based on the zeroth law of thermodynamics. An ideal-gas thermometer can be used to measure the absolute temperature, independent of the thermometer Muid, ‘The equilibrium state is one in which all forees are exactly balanced and any tendency for changes on a macroscopic scale is absent. The minimum number of intensive properties required to define such a state was provided by the phase rule, which links this number to the number ‘of components and the number of phases constituting the system. All naturally occurring processes ‘were shown to be irreversible. A system undergoing a reversible process can be brought back to its original state without any changes in the surroundings, Reversible process is an idealised concept that can be used for comparing the performance of actual processes. REVIEW QUESTIONS 1. Can thermodynamics help us to determine the maximum yield of a specified product in a chemical reaction? 2. Using thermodynamic principles, can you determine the rate of a chemical reaction? Why? 3. Iris suggested that by increasing the size of the furnace and thereby providing sufficient reaction time, the CO content in the effluent gases leaving a blast furnace can be reduced to zero. Comment on this suggestion. 4. Distinguish between system and surroundings. 8 What do you understand by homogeneous system and heterageneons system? Is the system consisting of an equimolar mixture of water and benzene at room temperature and pressure, homogeneous or heterogeneous? 6. Distinguish between closed system and open system. Say whether the following systems are closed or open: G@)_ A tubular reactor (b) A batch reactor (©) Individual phases in a multiphase system.Introduction and Basic Concepts 2 7. How would you define extensive and intensive properties? State whether the following properties are intensive or extensive: (a) volume, (b) density, (c) specific volume, (d) heat capacity, (e) specific heat, (1) potential energy, (g) pressure, (h) temperature. ‘8 Distinguish between state function and path functions with examples. A cyclic process ‘may he defined as the one in which after a series of changes, the system is brought back to its initial conditions, What would be the change in a state function in a eyclie process? 9. Why don’t we treat the potential energy and kinetic energy of a system as its thermodynamic properties? 10. What is zeroth law of thermodynamics? How is it helpful in measuring temperature? 11. Is it true that the temperature indicated by different devices would be the same only at the fixed points used for calibrating them? Why? 12. What is the importance of the ideal-gas temperature scale? 13, How are the efficiency of a heat engine and the COP of a heat pump defined? 14, What do you understand by thermal reservoies? 1S, Distinguish between steady state and equilibrium state, 16. The work done by the gas during expansion 0 be ealeuated from the properties ofthe ss as [ P-dV. Is it applicable to imevesible processes? 17. “A reversible process is never attained in practice. It ean only be approached.” What are the factors that make this statement true? 18 What do you mean by the number of degrees of freedom? What is the number of degrees of freedom when a binary liquid mixture is in equilibrium with its vapour? EXERCISES (In all the following problems, unless otherwise specified, take the gravitational acceleration to bbe 9.80671 mis?) 1.4 A man cireling the earth in a spaceship weighed 300 N at a location where the local gravitational acceleration was 3.35 m/s’, Calculate the mass of the man and his weight (on the earth, whete the gravitational acceleration is 9.81 mvs? 1.2. a man weighs 600 N at a place where the local acceleration due 10 gravity is 9.81 mis?, ‘what would be his weight on the moon, where the acceleration due to gravity is 1.67 ms2? 1.3. A special manometer fluid has a specific gravity of 3.65 and is used to measure a pressure of 1.25 bar at « location where the barometric pressure is 760 mm Hg. What height will the manometer fluid register? 1.4 A mercury manometer used for pressure measurement indicates $00 mm. The density of mercury is 13.56 x 10° kg/m? and acceleration due 10 gravity is 9.81 m/s?, Express the pressure indicated in bar LS What is the pressure exerted on a skin diver who has descended to 20 m below the surface of the sea, if the atmospheric pressure is 1 bar at the sea level and the specific gravity of the sea water is 1.03?A Textbook of Chemical Engineering Thermodynamics 16 M7 18 19 110 42 113 Lat 1s 1.16 ‘A mercury manometer used to measure pressure inside a vessel indicates 400 mm. One tend of the manometer is exposed to the atmosphere. The atmospheric pressure is 1.01325 bar. Density of mercury is 13.56 x 10° kg/m’ and g = 9.81 nvs?, What is the absolute pressure in the vessel in Ni ‘The potential energy of a body of mass 20 kg is 3.5 KJ. What is the height of the body from the ground? If a body of mass 20 kg is moving at a velocity of 50 m/s, what is its Kinetic energy? A car having a mass of 1200 kg is running at a speed of 60 km/h, What is the kinetic energy of the car in kJ? What is the work to be done to bring the car to a stop? A body of mass 50 kg is lifted through a distance of 15 m. What is the work done? If it took 2 min for lifting the mass, caleulate the power. ‘A man whose weight is 700 N takes 2.5 min for climbing up a stairease, What is the power developed in him, if the staircase is made up of 20 stairs each 0.18 m in height? ‘The steam supplied to an engine liberates 5000 J of heat. Ifthe engine efficiency is only 40 per cent, to what height a body of mass 10 kg can be lifted using the work output from the engine? Nitrogen gas is confined in a cylinder and the pressure of the gas is maintained by a weight placed on the piston. The mass of the piston and the weight together is 100 kg. ‘The acceleration due to gravity is 9.81 m/s* and the atmospheric pressure is 1.01325 bar. Assume frictionless piston, Determine: (a) The force exerted by the atmosphere, the piston and the weight on the gas if the piston is 200 mm in diameter (b) The pressure of the gas. () If the gas is allowed to expand pushing up the piston and the weight by 500 mm, what is the work done by the gas in kI? (@) What is the change in the potential energy of the piston and the weigh expansion in part (©)? ter the A spherical balloon of diameter 0.5 m contains a gas at | bar and 300 K. The gas is heated and the balloon is allowed to expand. The pressure inside the balloon is directly proportional to the square of the diameter, What would be the work done by the gas when the pressure inside reaches 5 bar? A body of mass 20 kg is dropped from a height of 15 m. What is the potential energy of the body at the time of its release? Assume that the potential energy gets converted into kinetic energy when the body strikes the ground. At what velocity does it strike the ground? A balloon which was originally empty is being filled with hydrogen from a cylinder at ‘constant temperature of 300 K. The atmospheric pressure is 1,01325 bar. What is the work done by the balloon-cylinder system when the balloon attains a spherical shape 6 m in diameter? Five kilograms of CO; gas is contained in a piston-cylinder assembly at a pressure of 7.5 bar and a temperature of 300 K. The piston has a mass of 6000 kg and a surface area of 1m? The friction of the piston on the walls is significant and cannot be ignored. The atmospheric pressure is 1.01325 bar. The latch holding the piston in position is suddenly removed and the gas is allowed to expand. The expansion is arrested when the volume is double the original volume. Determine the work done in the surroundings,FIRST LAW OF THERMODYNAMICS 2.41 GENERAL STATEMENTS OF FIRST LAW OF THERMODYNAMICS The idea of designing an engine that would produce mechanical work continuously without drawing energy from external sources and without undergoing a change had been a great fascination for scientists and engineers. The failure to construct such a perpetwal motion machine (PMM) formed the basis for the law of conservation of energy (H. von Helmholtz, 1847), The fundamental implication of this law is that “alshough energy may be converted from one form to another, it cannot be created or destroxed". Whenever a quantity of one form of energy is produced, an exactly equivalent amount of another kind must be used-up. When the law of conservation of energy was proposed, heat was not considered 10 be a form of energy. It was a series of experiments conducted by Joule between 1843 and 1847 that established heat as a form of energy. A known quantity of water taken in an insulated container ‘was agitated by means of a paddle wheel. The resulting temperature rise was noted. It was found that an exact proportionality existed between the amount of work expended on the water and the rise in temperature. The sume proportionality was obtained by the following different methods of transforming work into heat 1, The mechanical work was converted to electricity and the electric current was passed through coils immersed in water, 2. A gas confined in a cylinder immersed in water was compressed mechanically 3, Two metal pieces immersed in water were rubbed against each other by mechanical work The use of a given amount of work on a quan ssame temperature rise regardless of the way in wh established a between heat and work thus rejecting the earlier theory that treated heat as a substance. The recognition that heat and internal energy are forms of en ergy along with work, potential et kinetic energy and the law came to be known as first Jaw of thermodynamics, ‘The first law of thermodynamics is a generalisation based on our experiences like the failure to construct a perpetual motion machine, the constancy of mechanical equivalent of heat, etc. It is stated in a number of ways, but precisel gain of energy by the system must be exactly equivalent 10 the gain or loss of energy of the surroundings. For an isolated system—a combination of the system and the surroundings—the 2a ty of adiabatically enclosed water gave the ch the process was carried out, Joule's experiments juantitative relations led to their inclusion in the law of conservation of it means that energy is indestructible. Any loss orBa A Textbook of Chemical Engineering Thermodynamics total energy therefore, remains constant, although it may be changed from one form to another. ‘The universe can be treated as an isolated system and therefore we can say, "the energy of the universe is conserved”. 2.2 FIRST LAW OF THERMODYNAMICS FOR CYCLIC PROCESS Consider a static system undergoing a cycle of changes. Work is done on the system by forces acting from the surroundings, or vice versa, and heat is transferred between the system and the surroundings during the process, Then, according to the first law of thermodynamics, the algebraic summation of all work effects exactly equals the summation of all heat effects. Let Q denote the heat added to the system and W'the work done by the system (Q is negative when heat is rejected by the system and W is negative when work is done on the system) and if hoth are measured in consistent units, Ew @ If the units chosen for heat and work are different, the above equation can be written as EW=JEQ J is the mechanical equivalent of heat if the work is mechanical, and electrical equivalent of heat if the work is electrical, 2.3 INTERNAL ENERGY Heat and work represent energy in transit, Energy exchange between the system and the surroundings ‘occurs either as heat of as work. Heat and work are thus external effects of changes occurring ‘within the system or are external manifestations of stored energy. What happens 10 the state of the system after heat is supplied to it and before work is extracted from it? The system undergoes fa change because energy gets stored within it. The energy stored in the system by virtue of the configuration and motion of the molecules constituting the system is called its internal enere I is a definite property of the system and is denoted by U. The energy due to the mass motion of the system as a whole (the kinetic energy), and that {due to its external position in a gravitational, electrical, or magnetic field (the potential energy) are not included in the internal energy, U, as these forms of energy are not properties of the system. The molecules constituting the system possess kinetic energy of translation, rotation, and vibration. They also possess potential energy due to the forces of attraction existing among them. ‘These molecular potential and kinetic energies contribute t0 the internal energy of the system. ‘The addition of heat 1o the system results in the increase of its molecular kinetic energy and thus. increases the internal energy of the system. ‘A given system under a given set of conditions has a definite internal energy. In a cyclic process, the internal energy of the system after a series of changes remains the same as it was before. The heat and work involved in a non-eyelie process are not equal. Consequently, some ‘energy gets stored in the system or some stored energy gels removed from the system during a non-cyclie process. These changes in the stored energy are measured as the change in the internal ‘energy of the system. It should he borne in mind that it is impossible to measure the total internal ‘energy of a substance and therefore absolute values of internal energy are not known. This is notFitst Law of Thermodynamics [25] a serious limitation because it is the changes in intemal energy and not the absolute values that are usually needed in thermodynamic analysis. can be shown that internal energy is a thermodynamic property of the system and is solely determined by the thermodynamic state and not by the path by which that state was arrived at Consider a system undergoing a series of changes from state 1 to state 2 along path a as shown in Fig. 2.1. Let the initial conditions be restored along path b. If the surroundings remain unchanged, the change in internal energy (AU) along path a must be exactly equal but opposite in sign to that along path b. On the other hand, if AU along path b were less than that along path 4, there would be a residuum of energy resulting from this eyclic operation. Energy would have been created without loss of an equivalent amount of another kind, or in short, a PMM would have been possible. As this is contrary to the first law, the energy changes along paths @ and b should be numerically equal. By the same reasoning, it can be shown that AU along paths ¢ and 4 also should be numerically equal but opposite in sign to AU along path a. Here, paths b,c, and d are different routes for changing the state of the system from state 2 10 state 1. This means that the internal energy change accompanying a given change of state depends only on the end states and not on the path followed; that is, internal energy is a state function, Volume Pressure Fig. 2.1 Internal energy is state function, 2.4 FIRST LAW OF THERMODYNAMICS FOR NON-FLOW PROCESS ‘The first law of thermodynamics requires that the change in the total energy of the system be compensated by an equal but opposite change in the total energy of the surroundings, so that, there is no net change in the energy in any process. The change in the total energy of the surroundings occurs only through the exchange of heat or work with the system, Then the change in the total energy of the surroundings, (AE)aq, must be equal to the energy transferred 10 or from it as heat and work. Since Q is the heat transferred to the system and Wis the work extracted from it during the process, (AE) ue == + W ay For a closed system undergoing only changes in the kinetic, potential, and internal energies, the total energy change of the system (AE), is given by (AB), = A(KE) + A(PE) + AU 22)26 A Textbook of Chemi Engineering Thermodynamics Since (AB},y, = — (AE) ye We can combine Egs. (2.1) and (2.2) as follows. A(KE) + A(PE) + AU = 0- W 23) In the above equations A(KE) and A(PE) denote changes in kinetic energy and potential energy respectively. Equation (2,3) means that the total energy change in a closed system is equal 0 the heat added to the system minus the work done by the system. For a steady-state non-flow process in which there are no changes in the kinetic energy and potential energy, the above equation simplifies to aU=0-W 4) For differential changes in the thermodynamic state of a closed system, Eq. (2.4) can be written du = do -W 25) Equations (2.4) and (2.5) are the mathematical statements of first law of thermodynamics for non- flow processes. EXAMPLE 2.1 A system consisting of some fluid is stirred in a tank, The rate of work done fon the system by the stirrer is 2.25 hp. The heat generated due to stirring is dissipated to the surroundings. If the heat transferred to the surroundings is 3400 kJ, determine the change in internal energy Solution The work done on the system can be obtained as: 5(745.7) = 167.825 W = 1677.825 Is =W= 225 hp = Heat transferred to the surroundings is = @ = 3400 ksh = 3400 x 1043600 = 944.444 Vs By £4. (24), AU = Q ~ W = ~944.444 ~ (— 1677.825) = 733.381 Is ‘The internal energy of the system increases by 733.381 J in one second, EXAMPLE 2.2 on filings ate contained in a eylinder in an atmosphere of oxygen. It combines with oxygen according to the following reaction. 2 Fe + (3/2) 0; > Fe,0s ‘The pressure inside the cylinder is maintained at 101 kPa, The temperature is kept constant at 298 K hy removing heat. For 2 mol iron reacted, calculate Q, W, and AU given that 831.08 ki Of heat is liberated in the process Solution The heat liberated when 2 mol iron reacts with oxygen is 831.08 x 10° J. Therefore, =~ 831.08 x 10°F Neglecting the volume occupied by the solids, the volume change accompanying the process is ‘equal to the change in the volume of oxygen. Assuming ideal gas behaviour for the gas,Fitst Law of Thermodynamics [27] Pal (An) RT where AV is the volume change and An, the increase in the number of moles accompanying the reaction. Here An =~ 15. Therefore, the work done by the system, W = PAV = (An)RT =~ 1.5 Ri = 1.5(8.314) 298 = - 3716.41 ‘The change in the internal energy is AU = Q - W = ~831.08 10° (~ 3716.4) = ~ 827.364 x 10°) EXAMPLE 2.3. A cat riding downbill at a speed of 20 m/s was applied brake when it was at ‘a height of 30 m vertically above the bottom of a hill. When the car comes to a halt at the bottom ‘of the hill, how much energy as heat must be dissipated by the brakes, if wind and other frictional effects are neglected? The car weighed 1400 kg. Solution The first law of thermodynamies is given by Eq. (2.3) A(KE) + A(PE) + AU = - W Here A(KE) and A(PE) are the changes in kinetic energy and potential energy of the car respectively. ‘The kinetic energy of the car is (1/2) mu and the potential energy is mgz. The kinetic energy and potential energy of the car when it comes to a stop at the bottom are both equal to zero. Therefore, the changes in kinetic energy and potential energy are the negative of their respective initial values. Noting that m is the mass, w is the velocity and z is the elevation above the bottom of the Bill, MKB) = — (1/2) mu?, = ~ (1/2) 1400 (20°) = ~2.8 x 10° J A(PE) = ~ gc, = ~ 1400 (9.81) 30 = ~4.12 x 10°F ‘Therefore, = (-28x 10°) + (4.12 x 108) = - 6.92 x 1095 Hence, heat dissipated by the brakes = 6.92 x 10° ENAMPLE 24 4 system consisting of a gas confined in a cylinder is undergoing the following series of processes before it is brought back to the initial conditions: Step 1: A constant pressure process when it receives 50 J of work and gives up 25 J of heat : A constant volume process when it receives 75 J of heat Step Step 3: An adiabatic process. (Note: In adiabatic process there is no heat exchange between system and surroundings.) Determine the change in internal energy during each step and the work done during the adiabatic process. Solution The process is shown in Fig. 2.2, Step AB is a constant pressure process. Internal energy change for this step is calculated as (AU gp = Qua Wap =~ 25 + 50 During step BC, no work is done, as it is constant volume process. Change in internal energy is 25428 A Textbook of Chemi Engineering Thermodynamics Pressure gi_~+——~4 Volume Fig. 2.2. ilustration of processes in Example 2.4 (A0)uc= Onc = 753 Step CA being an adiabatic process, Oca (0c 0. Therefore, Wea For a eyelie process, the net ehange in internal energy is zero. That is, (AU) 5+ (AUdac+ AU) A=0 = {(AU) p+ (AU) gc] = = (25 + 75) =~ 1003 = (Ader (Ave Therefore, Wea, the work done during the adial 00 J. ic process 2.5 ENTHALPY For a system kept at constant volume in which no work of expansion or any other kind of work is done, the change in intemal energy is equal to the heat supplied to it. When the system is free to change its volume against a constant external pressure, the change in internal energy is no longer equal 10 the energy supplied as heat. In effect, a part of the energy supplied is utilised by the system for occupying a new volume; the energy thus utilised is equal to the work required to ‘push’ the surroundings against a constant pressure. Consequently, AU Cy. However, the difference between Cp and Cy for solids and liquids are very small compared to that for gases, as the change in volume of solids tand liguids during heating is not very significant Equations (2.17) and (2.20) give dU = Cy dP (constant volume) @21 4H = Cy dT (constant pressure) 2.22) For a constant volume process, change in the internal energy is given by Eq. (2.21). Since internal energy is a state function, Eq. (2.21) should give the change in intemal energy in any process, provided the initial and final volume are the same irrespective of the path along which thi change is brought about, However, Eq. (2.15) gives the heat required only for a process where the volume undergoes no change. Similarly, the change in enthalpy in a constant pressure process ‘or a process in which the initial and final pressures are the same, ean be evaluated by Eq. (2.22) whereas Eq, (2.18) determines the heat supplied in a true isobaric process only. ENAMPLE 2.11 Hydrogenation of an oil is carried out in a reactor at a pressure of 136.8 kPa and a temperature of 453 K. The hydrogen gas at 293 K is heated to 453 K by passing through coil where it experiences a pressure drop of 300 kPa. Hydrogen behaves like an ideal gas and its heat capacity at constant pressure is 29.4 ki/kmol, Neglecting kinetic energy effects determine the heat transier rate in the coils per 1000 kg hydrogen, Solution ‘The hydrogen gas at the inlet of the coils is at T= 293 K and P = 300 + 136.8 36.8 kPa and the hydrogen at the exit is at 7”= 453 K and P= 136.8 kPa, It is assumed that there is no pressure drop between the coil exit and the reactor, Neglecting the kinetic and potential energy changes the general first law equation, Eq. (2.13), reveals that the heat supplied is equal to the change in enthalpy of the gas. The enthalpy being a state function change in enthalpy can be calculated by assuming the actual process 10 be ‘occurring through a number of steps. Let us assume that in step 1, the pressure of the gas is being. reduced from 436.8 kPa to 136.8 kPa isothermally at 293 K, and in step 2, the gas is heated from 293 K 10 453 K at a constant pressure of 136.8 kPa. ‘The enthalpy of an ideal gas is dependent only on temperature. Thus, AH for step 1 = 0. For step 2 (02) 29.4 (453 ~ 293) = 2328.7 kJ Heat transferred in the coils, Q = AH = 0) + 2328.7 = 2328.7 ENAMPLE 2.12 Heat is wansferred 10 10 kg of air whieh is initially at 100 kPa and 300 K until its temperature reaches 600 K. Determine the change in internal energy, the change in enthalpy, the heat supplied, and the work done in the following processes: (a) Constant volume process (b) Constant pressure process, IRT, where nis the Assume that air is an ideal gas for which the P-V-T relationship is PV36 A Textbook of Chemi Engineering Thermodynamics 29.099 number of moles of the gas and is the ideal gas constant, R = 8.314 ki/kmol K. Take Cy KW/kmol K, Cy = 20.785 ki/kmol K and molecular weight of air = 29. Solution Number of moles of the gas = 10/29 = 0.3448 kmol. Py Hence, (00 kPa, T; = 300 K. RT [P, = 0.3448 (8.314) 300/100 = 8.6 m* 600 K @ Vz=86m', 7; Change in internal energy: AU = nf Cy dT = (0.3448) 20.785(600 ~ 300) = 2150 41 Heat supplied Q=AU = 2150) Work done W=0-au=0 Change in enthalpy AH = AU + A(PV) = AU + nRAT = 2150 + (0.3448) 8.314 (600 ~ 300) = 3010 kx ® P,= 100 KPa, T= 600K Change in enthalpy AH =n] Ce dP = (0.3448) 29,099(600 ~ 300) = 3010 KI Heat supplied Change in internal energy AU = AH ~ (PV) = AH ~ nRAT = 3010 ~ (0.3488) 8.314 (600 ~ 300) = 2150 K3 Work done: W=Q-AU = 860 [The work done may also be calculated as w PAV = PU - V)) Vs = nRTyP = 0.3448 (8.314) 600/100 = 17.2 m* ‘Therefore, w 00 (17.2 - 8.6) 860 KJ) EXAMPLE 2.13. The P-V-T behaviour of nitrogen is represented by the ideal gas equation PV = nT, where n is the number of moles of the gas and R the ideal gas constant (R = 8.314 kJ/kmol K). The heat capacities of the gas are Cy = 20.8 and Cp = 29.1 ki/kmol K. The gas initially at 10 bar and 280 K is undergoing a change of state to the final condition of | bar and 340 K. Determine the change in internal energy and the change in enthalpyFitst Law of Thermodynamics [37] Solution Take a basis of 1 kmol ideal gas, The initial conditions of the gas are represented by suffix 1 and the final conditions by suffix 2. P, = 10 bar, T; = 280 K. Therefore, Vy = ART YP, 28 m* 314 (28091000 = 2, 340 K, Therefore, RTH 314 (340y04 28,268 m? Since the changes in the state functions depend only on the terminal conditions and not on the path followed, we can assume that the actual change is carried out in different steps for which AH and AU are easily evaluated. Since the changes in U and H along @ constant volume and constant pressure paths are easily calculated using Cy and Cy, we may assume that the proposed change in state is occurring along the following two-step process: 1. A constant volume process in which the pressure is reduced to the final value P: and the temperature gets reduced 10 T’ Let P” and V‘ denote the pressure and volume of the system after this step. Then Par, VEY T= PVInR = 100 (2.328)/8.314 = 28 K For this constant volume process, AU = C\AT = 20.8128 ~ 280) 5241.61 AU + A(PV) = AU + VAP = ~ 5241.6 + 2.328(100 ~ 1000) = ~7336.8 kt w=o wv 5241.6 kl Q 2. A constant pressure process in which the gas is heated to the final temperature T; and the final volume Vs. For this constant pressure process, AH = CAT = 29.1340 ~ 28) H ~ PAV = 9079.2 ~ 100 (28.268 ~ 2.328) = 6485.2 kI 9079.2 ki AU = AH - APY) Q = AH = 9079.2) W = Q ~ AU = 9079.2 ~ 6485.2 = 2594 kI For the actual process, the changes in Vand JY are obtained as the sum of the respective values in the two-step process AU = 5241.6 + 6485.2 = 1243.6 KI AH = ~7336.8 + 9079.2 = 1742.4 KI38 Engineering Thermodynamics SUMMARY ‘The essence of the first law of thermodynamics is contained in the statement: “The energy of the universe is conserved” (Section 2.1). Mathematical expressions for the first law were developed for a statie system undergoing a cycle of changes (Section 2.2), for a non-flow process (Seetion 2.4), and for a flow process (Section 2.6). The internal energy U is a thermodynamic property arising by virtue of the configuration and motion of the molecules constituting the system (Section 2.3). Enthalpy H is defined as the sum of the internal energy that the system possesses and the product PV, the latter being the energy of the system by virtue of it occupying a space (Section 2.5). It was shown that for a cyclic process, the difference between the algebraic summation of all the heat effects and the summation of all the work effects is zero, whereas for non-flow processes, in general, the difference between the heat supplied to the system and the ‘work done by the system is equal to the change in its internal energy, The application of the first Jaw of thermodynamics to the steady-state flow through an equipment, in which the changes in the kinetic and potential energies were negligible, revealed that the difference hetween the heat and work effects accompanying the process could be measured by the enthalpy change in the process. Section 2.7 was devoted to the definitions of two very important thermodynamic properties used for the determination of the heat requirements in a process: the heat capacities at constant pressure and at constant volume, Cpand Cy, respectively. The heat requirement under the constant volume restriction is different from that in a constant pressure process, since in the latter, part Of the heat supplied is utilised for maintaining the pressure and is not available for increasing the temperature (Section 2.7). REVIEW QUESTIONS 4. What is the significance of Joule’s experiments in the formulation of the first law of thermodynamics? 2. “Energy can neither be created nor be destroyed”. How does this statement lead 10 the statement “The energy of the universe is conserved"? 3. What do you mean by a cyclic process? State and explain the first law for a cyclic process. 4. Distinguish between internal energy, kinetic energy. and potential energy of a system. ‘8. What is the change in internal energy in a eyclic process? What is it in a static non-flow process? 6, Prove that the internal energy is a state function. 7. What is enthalpy of a system? How is it related to the internal energy? '& Prove that the heat supplied is equal to the change in intemal energy for a constant volume process and the change in enthalpy for a constant pressure process, 9. What is meant by ‘entrance work’ in flow systems? 10. How do you state mathematically the first law of thermodynamics that can be used for solving steady-state fluid flow problems?Fitst Law of Thermodynamics [39] Te 2 2a 22 23 24 2s 26 27 Why is the specific heat at constant pressure, Cp, always greater than that at constant volume, Cy? For all processes, where the initial and final pressures are the same, dQ = dH = Cp dT. Do you agree? If not, why? EXERCISES An elevator with a mass of 2500 kg rest ata level of 7.5 m above the base of the elevator shalt It is raised to 75 m when the cable holding it breaks. It falls freely 10 the base where it is brought to rest by a strong spring. Assume that the acceleration due to gravity is 981 m/s*, Neglecting the effect of friction, Calculate: (a) The potential energy of the elevator in its initial position. (b) The potential energy of the elevator in its highest position. (¢) The work done in raising the elevator. (d) The kinetic energy and velocity of the elevator just before it strikes the spring. (e) The potential energy of the spring when the elevator rests on it Consider 1 kg of water in a waterfall which is flowing down from a height of 100m. At the bottom of the fall it joins a river the downstream velocity of which may be assumed negligible. Neglecting any energy exchange between the water and the surroundings, calculate: (a) The potential energy at the top of the falls. (b) The kinetic energy just before the water strikes the bottom. (¢) The change in temperature of the water when it centers the river. A 10 g lead ball at 300 K is dropped from a height of 10 m. Calculate: (a) the kinetic energy and speed of the ball as it reaches the ground and (b) the temperature rise of the ball if all its kinetic energy is transformed into internal energy as the ball is suddenly stopped after 10 m, given that the specific heat of lead is 125.6 J/kg K and its volume change is negligible ‘A miature of saturated steam and saturated water is contained in a rigid tank of volume 0.1 m' at a pressure of 2 bar. The liquid occupies 10% of the total volume, How much hheat must be added in order that the tank contains only saturated steam? What will be the pressure in the tank? The specific volumes of saturated liquid and saturated vapour are 1.061 x LO” m'vkg and 0.8857 m'vkg respectively, The intemal energy of saturated liquid and saturated vapour are respectively 504.5 ki/kg and 2529.5 kifkg. Iron reacts with hydrochloric acid at 300 K according to FeS (s) + 2HCI (ag) FeCl (ag) + Hs (8) Determine the work done when 0.1 kg iron reacts with HCI in (a) a closed vessel, (b) an open vessel A vessel of volume 1 m? initially contains one per cent by volume saturated liquid water and the rest saturated vapour at 1 bar. How much heat is to he supplied so thar the vessel gets filled with vapour? Take data from steam tables. Liguid water at 373 K and 101.3 kPa has an internal energy of 420 ki/kg on an arbitrary basis, The specific volume at these conditions is 1.04 x 10° m'kg. The water is brought40 28 29 2.10 2a 242 243 24 A Textbook of Chemi Engineering Thermodynamics to the vapour state at 473 K and 700 kPa. At this condition, its specific volume is 0.3 m'vkg. and its enthalpy is 2844 kifkg. Calculate the enthalpy of the liguid and the changes in intemal energy and enthalpy accompanying the vaporisation process. A sample of 10 g of liquid benzene at its boiling point is vaporised using a 12 V, 0.5 A electric supply. The normal boiling point and latent heat of vaporisation of benzene are 393.2 K and 30.8 x 10° ki/kmol respectively. Determine: (a) the change in internal energy, (b) the time required for complete vaporisation, A cylinder fitted with a piston has a volume 0.1 m° and contains 0.5 kg of steam at 500 kPa, How much heat is to be supplied to bring the temperature of the steam to 823 K keeping the pressure constant? What is the work done in the process? A steam boiler of volume 2.3 m? initially contained 1.7 m* liquid water in equilibrium th 0.6 m° of vapour at 100 kPa. The boiler is heated keeping the inlet and discharge valves closed. The relief valve is set to lift when the pressure in the boiler reaches 5500 kPa. Determine the amount of heat supplied to the contents in the boiler before the relief valve lifts, A gas expands from an initial volume of 0.2 m* toa Final volume of 0.4 m* in a reversible steady flow process, During the process, the pressure varies with the volume as P=SxIOV47x 10" where P is in N/m? and Vis in m?, The inlet line is 4 m below the outlet Tine and the gas enters with a negligible velocity. The internal energy of the gas decreases by 30 KI during the process. Determine the heat transferred. A trial run on a steam turbine power plant gave the following results Entrance to boiler Exit of turbine Mass flow rate = 3600 kg/h Velocity of steam = 25 m/s Enthalpy of water = 850 kW/kg Elevation above datum = 0 Elevation above datum 43m Enthalpy of steam = 2625 ki/kg Velocity of water = 5 m/s Determine the power developed by the turbine if the heat added in the boiler is 2100 kis, ‘The work required for compressing a gas from an initial condition of 100 kPa and 300 K to a final pressure of 300 kPa is found to be 280 kl/kg of the gas. The compressed gas is admitted to a nozzle where its velocity is increased t 700 mis. If the gas enters the compressor with negligible velocity and leaves the nozzle at 100 kPa and 300 K. what is the heat removed during compression? In a test of water-jacketed air compressor, it was found that the shaft work required (0 drive the compressor was 150 Ki/kg air compressed. The enthalpy of air leaving the compressor was found to be greater than that of the air entering the compressor by 80 kW/kg and the heat removed by the cooling water was 100 ki/kg of air. Determine the amount of energy that must have been dissipated as heat (© the atmosphere from the bearings, cylinder walls, eteFitst Law of Thermodynamics (ay) 2.18 Water at 200 kPa and 355 K (H = 343.3 ki/kg) enters a straight horizontal pipe at a velocity 3 m/s where itis heated by flue gases from the outside. Steam leaves the system at 100 kPa and 423 K (= 2776.3 kl/kg) at a velocity of 200 mvs. How much heat must have been supplied per ke of water flowing 2.16 A steam-jet ejector is used to entrain saturated water vapour at 25 kPa (H = 2618.2 ki/kg) leaving an evaporator, by high pressure saturated steam at 1000 kPa (2778.1 ki/kg). It is estimated that with every kg of high-pressure steam 0.75 kg of the vapour from the evaporator can be entrained, If the mixed stream leaving the ejector is at 100 kPa what is its temperature? 2.17 Oil flows at a rate of 1000 kg/min from an open reservoir at the top of a hill 400 m in height to another reservoir at the bottom of the hill. Heat is supplied to the oil on i ‘way al the rate 1800 ki/min and work is supplied by a 1 hp pump. Take the mean speci heat of oil to be 3.35 ki/kg K. Determine the temperature change of the oil 28 A gas initially at 100 bar is undergoing a reversible process in which its pressure gets doubled at a constant volume of 0.5 m’. If the total internal energy (U') of the gas in KJ is related to the pressure P in bar and total volume (V/) in m! according to U" = 2.0 PV’, ealeulate the change in enthalpy and the heat supplied, 2.19 (a) Three kilo mole nitrogen gas (Cp = 29.1 k¥/kmol K and Cy = 20.8 ki/kmol K) at 350K is taken in a rigid container and is heated to 550 K. How much heat must be supplied, if the mass of the vessel is 100 kg and its specific heat is 0.5 ki/kg K? (b) ‘Two kilo mole nitrogen is taken ina piston/eylinder arrangement at $00 K. Determine the quantity of heat extracted from the gas to cool it 350 K at constant pressure if the heat capacity of the container is: negligible 220 An insulated rigid container contains ait at S bar and 375 K. The volume of the container is I'm’, Air may be assumed to behave as an ideal gas so that the P-V-T relationship is PY = nkT, where R = 8.314 kifkmol K. The specific heat Cy of air is 20.785 kifkmol K The temperature of the air is increased by a rotating paddle wheel. Calculate the work done to raise the temperature of the air to 425 K 221 Assume that the P-V-T relationship for nitrogen gas ean be approximated by the ideal gas equation PV = nT, where R = 8.314 ki/kmol K, The heat capacities are Cy = 20.786 KJfkmol K and Cp = 20.1 ki/kmol K. Nitrogen which was initially at 1 bar and 280 K, is compressed to 5 bar and 280 K by two different reversible processes: (@) Cooling at constant pressure followed by heating at constant volume (b) Heating at const volume followed by cooling at constant pressure, For each of the above paths, determine the conditions at the intermediate state and AU, AH, Q and W. 2.22 One kilo mole of gas for which PV = nRT, where R = 8.314 ki/kmol K is originally at 300 K and J bar, It is then heated at constant pressure to a temperature of 400 K and compressed isothermally to a volume equal to its initial volume, Assume that Cp = 30 ki/kmol K. Find AU, AH, Q and W.P-V-T BEHAVIOUR AND HEAT EFFECTS 3.1. P-V-T BEHAVIOUR OF PURE FLUIDS ‘The thermodynamic state of a pure fluid can he described in terms of two independent properties. Consider the thermodynamic state of a one component system, for example, water, which is represented in Fig, 3.1 as a function of pressure and volume. The figure shows the variation in molar volume with pressure at various constant temperatures. Assume that the initial state of the system is represented by point a The change in volume of water with pressure at a constant temperature 7; is along the isotherm a-b-d-e. Since liquid water is almost incompressible, reduction in pressure for the change of state from @ to b produces only negligible increase in volume. When point b is reached, vaporisation begins and this results ina rapid increase in volume, From 6 to d, the wo phases, liquid and vapour, are in equilibrium, The temperature and pressure remain constant during the phase change as indicated by the horizontal portion of the isotherm b-d. The saturated liquid state is represented by point b and the saturated vapour state by point d. The relative amounts of the vapour and liquid phases in equilibrium change with continued vaporisation, and at point d, the entire liquid has been vaporised. The vapour and Tiquid coexisting in equilibrium are called saturated phases. Points along the horizontal line b-d represent all possible mixtures of liquid and vapour, with point b representing saturated liquid he Fig. 3.1 P-V-T behaviour of pure fluids (e.g. water) 2P-V-T Behaviour and Heat Effects [a3] state (100% liquid) and point d saturated vapour state (100% vapour). The pressure at which the liquid and vapour phases coexist in equilibrium is called the saturation pressure, and the temperature corresponding to this pressure is called the saturation temperature. Further reduction in pressure increases the volume of the system along the curve d-e. When the pressure over the system is brought down to a value less than the saturation pressure at constant temperature oF when the temperature is increased above the saturation temperature at constant pressure, the vapour gets superheated, We see that the P-V isotherm has two discontinuities in its slope at points b and d. The isotherm at a higher temperature T will be similar to that at temperature 7,, but the length of the horizontal seetion joining the saturated Tiquid and vapour phases will be smaller. The locus Of the saturated phases is represented by the dome-shaped eurve b-e-d. The atea under this dome represents the two-phase region, the area to the left of curve ac is the liquid region, and the area to the right of curve e-d is the vapour region, When the temperature of the system is inereased to To, the critical wemperature, the discontinuities disappear indicating that, at the critical temperature, the saturated liquid and saturated vapour phases become indistinguishable. The liquid state changes to vapour state without any discontinuity at the eritieal point represented by point c in the figure. The properties Of the substance at the critical point are known as critical properties. The critical properties of water are Te-= 047.3 K, Pc = 220.5 bar and Ve = 56 x 10° m'/mol. The eritical temperature and critical pressure represent the highest temperature and pressure respectively, at which a pure ‘material can exist in vapour-liquid equilibrium. If the temperature is less than the eritical temperature, the substance t0 the right of the saturated vapour Tine is called a vapour and, if the temperature is above the critical temperature, the substance is called a gas. A vapour can be condensed (0 a Tiquid by compression at constant temperature or by cooling at constant pressure ‘whereas a gas can be condensed by a reduction of temperature at constant pressure only. It cannot he condensed by compression at constant temperature. Ifthe temperature and pressure are geeater than Teand Pe respectively, the substance is in the fluid region and it can neither be condensed by any of the above methods nor ean it be vaporised by reduction in pressure as is possible with liquids. The substance in this state is neither a gas nor a liquid, ‘The phase behaviour of pure fluids ean be represented on PT diagram as in Fig. fn the isothe which Liquid Prossure ‘Temperature Fig. 3.2. Pressure-temperature diagram for a pure materiala4 A Textbook of Chemi Engineering Thermodynamics includes the solid region also, Consider unit mass of ice at pressure and temperature corresponding to point p in the figure. When it is heated at constant pressure, the temperature increases and at point q ice starts to melt. The temperature corresponding to point q is the fusion temperature. The Tusion Fine represents the state of the system at which the solid is in equilibrium with the liquid, If transfer of heat is continued, the temperature remains constant till the entire solid is liquefied. The fusion temperature is a function of the pressure only. If heating is continued, the substance centers the Fiquid region, and when it attains the temperature corresponding to point r lying on the vaporisation curve, the liquid begins to vaporise. When all liquid has been vaporised, temperature inereases along the line rs in the vapour region. Heating beyond the critical temperature Tetakes the substance into the gas region, The fusion curve and the vaporisation curve meet at the triple point where the three phases coexist in equilibrium. According to the phase rule, the triple point is invariant. For water at the triple point, T= 273.16 K and P = 6.1 x 10” bar. If the pressure of the system is below the tiple point pressure, the heating of the solid results in sublimation, i.e. the wansformation of solid directly into vapour. The sublimation curve in Fig. 3.2 represents the state of the system in which the vapour is in equilibrium with solid. It may be noted that the fusion curve extends up to infinity whereas the vaporisation curve terminates at the critical point 3.2 EQUATIONS OF STATE AND THE CONCEPT OF IDEAL GAS ‘The thermodynamic state of a single homogeneous fluid may be specified by properties such as pressure, temperature, and volume. An equation of state is a functional relationship between these three variables and it may be written as JPN.) Ga) ‘The most simple equation of state is the one applicable for ideal gases. On a molecular level, an ideal gas may be treated as the one for which (a) the size of the molecules is very small compared to the distance between them so that the yolume of the molecules is negligible in comparison with the total volume of the gas and (b) the intermolecular forces are negligibly small. Thermodynamics characterises an ideal gas as the one for which the following properties are applicable: 1. Por one mole of an ideal gas the equation of state is given by PV= RT 2) where R is known as the ideal gas constant, Its value is 8.314 Mmol K. 2. The internal energy of an ideal gas depends only on temperature. It is independent of pressure and volume. 3) ‘The increase in temperature of an ideal gas results in increased kinetic activity of the molecules, which is manifested as an increase in its internal energy. When the gas is compressed at constant temperature, it will offer no resistance and consequently resulls in no change in its energy, as there are no intermolecular forces to overcome.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.P-V-T Behaviour and Heat Effects [a9] Using Eq. (3.20), Eg. (3.19) ean be rewritten as av at > Oe 21) Let the pressure, volume, and temperature are respectively P\, Vj. and 7; in the initial state of the gas and P,, V; and T; respectively be the corresponding values in the final state after the adiabatic process. Equation (3.21) on integration between the initial and final conditions gives which on rearrangement leads to the following relation between temperature and volume in an adiabatic operation: nm (Myo z ( ] 82) 1 va Using the perfect gas law, the ratio of volumes can be eliminated from Eq. (3.22) in favour of the ratio of pressures. My WOR ‘The resulting expression, Eq. (3.23), is the relationship between pressure and temperature in an adiabatic process involving ideal gases. \r-tvr h (F] 623) ‘Compare Eq. (3.22) with Eq, (3.23). Then PV? = constant 24) ‘The work done in the adiabatic process is given by Eq, (3.18). Since Cyis constant, Eq, (3.18) can be readily integrated. W= CT -T) 3.25) Equation (3.20) can be used to eliminate Cy from this equation in terms of %30 A Textbook of Chemi Engineering Thermodynamics = RTA RT, _ BY = BW, yt y-l w Equation (3.26) gives the work done in an adiaba into a more useful form as follows: je process involving ideal gas. This “That is, 627 3.3.5 Polytropic Process In a polytropic process, the relationship between pressure and volume is assumed 1 be PY" = constant, where m is a constant. If m = 0, the process is isobarie: the process become isothermal; and if n = ©, the process is isochorie (constant volume). If n= 7, the process is an adiabatic process. Generally the value of 1 lies between 1 and 7 indicating that the process lies between isothermal and adiabatic. In this case, the heat and work involved in the process ate to be calculated using the first law of thermodynamics and the relationships applicable for ideal gases. Equations (2.5), (3.6) and (3.11) may be used for this purpose along with the expression dW = PdV which gives the work of expansion in any reversible process dU = dQ -aw (25) aU = Cyt G6) dH = Cpa BLD ENAMPLE 33 An ideal gas is undergoing a series of three operations: The gas is heated at constant volume from 300 K and 1 bar to a pressure of 2 bar. It is expanded in a reversible adiabatic process to a pressure of 1 bar. It is cooled at constant pressure of 1 bar to 300 K. Determine the heat and work effects for each step. Assume Cy = 29.3 ki/kmol K. Solution The difference between Cp and Cy of an ideal gas is equal to R, the ideal gas constant. Hence Cy is given by cy Cp~ R= 29.3 ~ 8.314 = 20.986 ki/kmol K Step I: Volume remains constant. Therefore, work done is zero and heat supplied is Cy ¢ Also, TT = PJP; = 2; That is, T). 2x 300 = 600 KP-V-T Behaviour and Heat Effects (54) where T; is the final temperature attained. Heat supplied is 20.986 x (600 ~ 300) = 6295.8 ki/kmol Step 2: The process is adiabatic. Therefore, heat supplied is zero. ‘The work done is given by Eq, (3.25) as We Cy(T\-T) where T; and T; are the initial and final temperatures in the adiabatic process which are related 10 the initial and fi Therefore, 2.2K 00 x ay” W = 20.986 (600 ~ 492.2) = 2262.3 ki/kmol Since W is positive, work is done by the system. Step 3: The process is isobaric. Heat supplied is calculated as, Colts ~ 1) 29.3 (300 ~ 492.2) = ~ 5631.5 ki/kmol (Heat is given out by the system), AU = Cy(Tz ~ T)) = 20.896(300 ~ 492.2) = - 4016.2 ka/kmol First law states that AU = Q ~ W. Hence, W= Q ~ AU = ~5631.5 + 4016.2 = ~ 1615.3 kifkmol So, work is done on the system, EXAMPLE 34 Calculate the change in internal energy, change in enthalpy, work done, and the heat supplied in the following processes: (a) An ideal gas is expanded from 5 bar to 4 bar isothermally at 600 K. (b) An ideat gas contained in a vessel of 0.1 m? capacity is initially at 1 bar and 298 K. It is heated at constant volume to 400 K. (Assume that Cp = 30 Jmol K.) Solution (a) Since the internal energy and enthalpy of ideal gas depend only on temperature, in an isothermal process, they remain constant. AU = AH = 0. Equation (3.16) is used to calculate the work done and heat supplied. 4 = We Rr In B= 8314 x 600 In 5 = 1113.13 kirk!2 A Textbook of Chemi Engineering Thermodynamics (b) Number of moles of the gas is = PVIRT = (1 x 10°) 0.148.314 x 298) = 4.04 mol Cys Cp R= 30 ~ 8314 = 21.686 fmol K AU = Gy (Ty ~ T)) = 21.686 (400 ~ 298) = 2212 Smol = 2212 (4.04) = 8936 J AH = Cp (T; ~ 71) = 30(400 ~ 298) = 3060 J/mol = 3060(4.04) = 12362 J Being « constant volume process, W = 0, and O=au+W=au 936 J EXAMPLE 38 Twenty kilograms of air is compressed from 1 bar, 300 K to 5 bar in a single stage compressor. The process is polytrapic with m = 1.25. The specific heat of air at constant pressure in ki/kmol K or 27.4528 + 6.1839 x 10° T— 8.9932 x 107 Determine: (a) The work done by the compressor per eycle and (b) The amount of heat transferred to the surroundings. Solution Molecular weight of air may be taken as 29, Dividing the mass of air by the molecular weight, the number of moles can be determined, Number of moles of air = 20/29 = 0.69 kmol Initial volume of air is ARTIP = (0.69 x 10°) 8.314 (300\(1 x 10 ‘The pressure and volume in a polytropie process are related as aut (a) Work done: = 07456 ¢P-V-T Behaviour and Heat Effects [53] ‘Therefore, W = ~ 0.7456 (3.5028 x 10% = ~2.612 x 10°F ‘That is, 2612 kI of work is required by the compressor. (b) Amount of heat AM EM a3 MB ak Ay OT Ta The actual process is occurring along a polytropie path from the initial state at which the conditions are P= 1 bar, V= 17.21 m* and 7= 300 K to the final state where P= 5 bar, V= 4.75 m', and T= 414 K. This process may be assumed to ovcur in two steps 1. A constant temperature process at 300 K whereby the pressure is increased from 1 bar to 5 bar, 2. A constant pressure process at 5 bar by which the temperature is increased from 300 K to 414K, ‘The change in the internal energy for the actual process is equal to the sum of the internal energy cchanges in these two steps. The step | being an isothermal process AU = 0. For step 2, avef car Thus, the change in the internal energy of the actual process is av=[ cvar=f tcp—mare [i erases 46.18% x Wr 9992 x 10°F? R319 ar au 19.1388 (414 ~ 300) + (1/2) (6.1839 x 10°) 420.3 I/mol 2420.3 (0.69 x 10°) J = 1670 kd = (13) (8.9932 x 107) (414° — 300°) supplied: Q= AU + W= 1670 ~ 2612 =~ 942 kt ‘This means that heat is liberated in an amount equal 10 942 Ki. 3.4 EQUATIONS OF STATE FOR REAL GASES Perfect gas law is inadequate to explain the behaviour of real gases. For real gases to behave ideally, the molecular interactions should be negligible. At low molar volumes or high pressures, molecules come very close to each other and molecular interactions cannot be neglected. The periect gas law may be viewed as an approximation to describe the behaviour of real gases at ordinary pressures or as the limiting hehaviour of real gases at low pressures, Many equations of state have heen proposed to explain the actual behaviour of gases.34 3.44 Li ‘An equation of state, in general, should satisfy certain limiting conditions. They are 1. All equations reduce to the ideal gas equation at low pressures. That is, PV=RE as P30 ‘The slope of the PV isotherm against P may be equal to, greater than, or less than zero as pressure tends to zero. This is true for the slope of the compressibility factor versus P curve also. That is, either FY) oy xy [222] <0 ae 0 P AY) 29 asp 0 a |, 3. The P-V curve at constant temperature should exhibit a point of inflection atthe critical, point (F 28) 4, The P-T curves are linear except at very high densities. (= (or) This relation is exact as T > >» and is approximate at other conditions. However, at high 2) co or) ‘This inequality means that the P-T' curves are convex upward from the T-axis. A few of the commonly used equations of state are discussed in the following sections, 3.4.2. van der Waals Equation van der Waals proposed the following equation to explain the P-V-T behaviour of real gases. W -b=RT where a and b are called van der Waals constants. This equation is cubic in volume and belowP-V-T Behaviour and Heat Effects [55] the critical temperature, there are three real roots. The largest is the vapour volume and the smallest the liquid volume. The intermediate root has no physical significance. When P is the saturation pressure, the smallest and the largest roots correspond to molar volumes of saturated liquid and saturated vapour respectively. ‘The perfect gas equation fails to explain the P-V-T behaviour of real gases as the volume occupied by the molecules of a real gas and the forces of interaction between them are not negligible as in an ideal gas. van der Waals equation takes into account these two features of areal gas by incorporating certain correction factors in the pressure and volume terms ofthe ideal ‘208 equation, In order to find a correction term to compensate for the attractive forces between molecules, consider the forces of attraction on a molecule hitting the wall of the container. When the molecule hits the wall it experiences a net attractive force towards the surrounding molecules, thereby, reducing the pressure that would have been exerted by the molecule on the wall in the absence of intermolecular attraction. This attractive force is directly related to the number of molecules per unit volume and the frequency of molecular collision, the latter in turn being proportional to the number of molecules per unit volume. In short, the net attractive force proportional to /V? where V is the molar volume of the gas. The actual pressure, P, of the gas is less than the ideal pressure calculated by kinetic theory by a/V2, where a is a constant. Or, the pressure term in the ideal gas equation should be replaced by P + (a/V?) ‘The centres of two identical molecules are at a distance equal to the molecular diameter at the instant of their collision with each other. The molecular separation at collision cannot be smaller than this distance. Since each molecule is surrounded by a forbidden volume that cannot be penetrated by another molecule, the effective volume of the gas will be less than the actual volume, The volume term in the ideal gas eyuation is replaced by V~b, where b indicates the forbidden volume per mole of the gas. Equation (3.29) results by incorporating these corrections to P and V terms in the ideal gas equation PV = RT. v ‘The constants in the van der Waals equation can be evaluated utilising the limiting condition Ig, (3.28)] to he obeyed by any equation of state. Applying this criterion in Eq. (3.29), we get 8a 27 Rb Rle__a 2 oH 3h Te The last two identities can be solved to get the van der Waals constants as 3.30) EXAMPLE 3.6 One kilo mol COs occupies @ volume of 0.381 m* at 313 K. Compare the pressures given by (a) Mdeal gas equation (b) van der Waals equation ‘Take the van der Waals constants to be a = 0.365 Nuv“fmol” and b = 4.28 x 10° mmol36 A Textbook of Chemi Engineering Thermodynamics Solution ‘The molar volume of CO, is V = 0.381 x 107 mmol (a) Heal gas equation: P = RTIV = 8.314 (313)(0.381 x 107) = 68,30 x 105 Nim? = 68.30 bar (b) van der Waals equation: Equation (3.29) may be rearranged as pa SE v-b ve 8.314 G13) 0365 © O.381x 107) — 0.428 x10) 381 x 10)? = 518 x 10° N/m? = $18 bar EXAMPLE 3.7 Calculate the volume oceupied by one mole of oxygen at 300 K and 100 bar using (a) The ideal gas law (b) The van der Waals equation. Take a = 0.1378 N mmol? and 6 = 3.18 x 10 m*/mol Solution (a) Using the ideal gas equation, V = RTIP = 8.314 (300) x 10”) (b) Volume can be determined using Eq. (3.29) by a trial and error procedure. Assume a value for V and evaluate the left hand side of the van der Waals equation. If the value assumed is the correct one, A in the following equation will be zero. 0.249 x 10° m? (rez = by - Raa z Otherwise, repeat the calculation till A becomes equal to zero. The ideal gas volume may be ‘chosen for the first trial, The results of a few such calculations are given below: Vm Oa2x 10? 024x107 0.23 x 107 4 16 +859 4 ‘The molar volume of oxygen by the van der Waals equation = 0.23 x 10 m*/mol. 3.4.3 Redlich-Kwong Equation ‘The Redlich-Kwong equation (1949) is a two-parameter equation of state widely used in engineering calculations, TOV +b) gaya You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.P-V-T Behaviour and Heat Effects [es] Sum of the heat of combustion of products is ~890.94 kJ. By Eq. (3.44), 749 KI Auf? = —965.84 + 990.94 EXAMPLE 3.11 Using Hess's law, calculate the heat of formation of chloroform (CHCI,) with the following given data \ fa) CHC, (@) + £0, (@) #50 () 4 C05 (+ 3 CI (EA = ~500.93 Kd 1 (b) Hy (g) + 502 (2) > HLO (sly = —296.03 bd (©) € (9) #05 (@) > COs a); Athy = -393.78 kd (a) Lite) + Ech, Ge) + HCI (a): Avy =~ 167.57 i Solution Apply the following operation: Eq, (©) + 3 x Eq, (d) ~ Eq. (a) ~ Bq. (b) The following equation result lined , cr bins Sch Hels Af m=? Accordingly, the heat of formation would be — 303.78 + 3(- 167.57) + 509.93 + 296.03 = -90.53 kJ/mol 3.6.5 Effect of Temperature on Standard Heat of Reaction Consider the reaction A + DB > IL + mM Here, a, b, |. m are called stoichiometric coefficients. This reaction may be written as IL + mM ~ aA ~~ bB=0 in which ~ a, ~ b, 1, m are called stoichiometric numbers. Denoting the stoichiometric numbers Of the species taking part in a chemical reaction by vj, a chemical reaction in general may be represented by Zua G45) Here vis positive for products and negative for the reactants. For a chemical reaction represented by such general equation, how would you determine the standard heat of reaction at temperature Tif the standard heat of reaction is given at temperature 7,? The actual reaction occurring at heat of reaction is Ay, may be treated as occurring in three temperature 7, for which the standa steps as depicted in Fig. 3.5(66) A Textbook of Chemical Engineering Thermodynamics Reactant at 7 — — Products at 7 Reaction at 7, AH? 1 Cooling the Heating the products AMT, § iy ’ fs stants at 7,1_Reetion at 7. Ady Pe Products at 7) Fig. 3.5. Effect of temperature on heat of reaction. ‘The reactants are cooled from temperature T to 7). The enthalpy change for this step is AH, Zo fl neaT= S Jf wee ar G46) ests Reson 1 “The reaction is allowed to occur at temperature T;. The enthalpy change is AH, = AH, G47) ‘The temperature of the products is raised ftom 7; to T im this step. The enthalpy change is The standard heat of reaction at temperature 7, is obtained by adding the preceding three equations. Ad} = AH, + AH, + A, = 2 fica ar eann® Sf vey ar The above result ean be written as ant «ait + [° [Evce, 49) ‘The summation in the above equation is overall species taking part in the reaction. Let the heat capacity of the substances be represented by the following equation, G at p+ yP 3.50)P-V-T Behaviour and Heat Effects [67] Utilising Eg. (3.50), Eq, (3.49) can be writen as An} =AH} +f" 8 Cpa G51) where ACp= Mat (APT + (Ap TF G52) and Aa=Evya, AB=Evp and ay=Euy 853) Equation (3.51) may be expanded as Sip = at, + Acar —T) + ap? — 72) +L ay ‘The constants appearing in the above equation can be grouped together to single constant AK’, so that we have aw ans sats Be, ee G54) ‘The constant AA in the above equation can be evaluated ifthe heat of reaction at a single temperature is known, Equation (3.54) can now be used for the evaluation of the standard heat of reaction at any temperature 7. EXAMPLE 342. For the following reaction the standard heat of eation at 298 K is 164.987 CO (2) + 4 Hy (g) > 2 H:0 (g) + CH, (a) ‘The constants in the heat capacity (I/mol K) equation, Eq, (3.50), are given below: a B 7 CO, 26.75 42.26 x 10% 14.25 x 10 A 26.88 435x109 0.33 x 10% 0 29.16 1449x107 2.02 x 10% om 13.41 7203 x10 —_-18.74 x 10° Caleulate the standard heat of reaction at 773 K. Solution Equation (3.54) relates the heat of reaction to temperature. Aar= 2X 29.16 + 13.41 = 26.75 = 4 x 26,88 = - 62.54 Afi = (2 x 14.49 + 77.03 ~ 42.26 — 4 x 4.35) x 10% = 46.35 x 107 Ay= (2 x 2.02 - 18.74 + 14.25 + 4 x 0.33) x 10° =-7.21 x 1068 A Textbook of Chemi Engineering Thermodynamics Equation (3.54) gives 46.35 x 107) 21x 10% 2 3 AUT = 208 K and Alf = 164.987 10". the above equation gives AAT =~ 148345 J 50 that Af = AH’ 6254+ r gif =~ 148349 — 62.54 T+ 23.17 109 7 2.403 x 10% Putting T= 773 K in this equation, we get Ay, = 183950 J = — 183.950 kJ. EXAMPLE 3.13. Pure CO is mixed with 100 per cont excess air and completely bummed at constant pressure, The reactants are originally at 400 K. Determine the heat added or removed if the products leave at 600 K. The standard heat of reaction at 298 K is 283.028 kJ per mol CO burned. The mean specific heats applicable in the temperature range of this problem are 29.10, 29.10, 29.10, and 41.45 Imol K respectively for CO, Os, No, and COs respectively. Solution Basis: | mol CO reacted. al CO++0; C0, 702-9 COs Oxygen theoretically required = 0.5 mol ‘Oxygen supplied = 1 mol (100 per cent excess) Nitrogen in the air supplied = 1 x 79/21 = 3.76 mol Let AH; be the enthalpy of cooling the reactants from 400 K to 298 K. The reactants stream contains | mol oxygen, 3.76 mol nitrogen, and | mol CO. AM, = (1 x 29.70 + 3.76 X 29.10 + 1 x 29.10)(298 ~ 400) = ~ 17.158 KI Let AH; be the enthalpy of heating the products from 298 K to 600 K. The product stream contains 1 mol CO;, 0.5 mol oxygen, and 3.76 mol nitrogen. AM, (1 x 41.45 + 3.76 x 29.10 + 0.5 x 29.70}(600 ~ 298) = 50.046 Kd AH = AH, + AMDyg + AH, = — 17.158 ~ 283.028 + 50.046 250.14 KI 3.6.6 Temperature of Reaction A reaction is termed an adiabatic reaction if there is no heat interaction between the reaction ‘mixture and the surroundings. If the reaction is exothermic, the heat liberated during the reaetion will be utilised (© increase the enthalpy of the products, as no heat is removed to maintain the temperature constant, The products get heated up and the temperature attained is termed the temperature of the reaction. When a fuel is burned in air or oxygen under adiabatic conditions the temperature attained by the system is known as the adiabatic flame temperature. The maximum adiabatic flame temperature is attained when the fuel is burned in theoretically required amount Of pure oxygen. The adiabatic flame temperature attained when the fuel is burned in air or ex: oxygen, is less than the theoretical maximum flame temperature attained in oxygen,P-V-T Behaviour and Heat Effects [eo] Denoting as before, the enthalpy of cooling the reactants from temperature T, to 298 K by Ad, and the enthalpy of heating the products from 298 to T, the adiabatic flame temperature, by Aly, we can write AH MH) + AHS, + AH, Here AW is the difference between the enthalpy of products and the enthalpy of reactants, oF simply, the heat added or removed during the reaction, For an adiabatic reaction, this quantity is zero, and therefore, ffs =~ Att, ~ Alt 655) Equation (3.55) may be used to evaluate the temperature attained in an adiabatic reaction, EXAMPLE 3.14 Calculate the theoretical flame temperature for CO when burned with 100% ‘excess air when both the reactants are at 373 K. The heat capacities (J/mol K) may be assumed ‘constant at 29.23 for CO, 34.83 for Os, 33.03 for No, and 53.59 for CO>. The standard heat of combustion at 298 K is ~ 283.178 ki/mol CO. Solution Basis: | mol CO, L co+40, 00, Reactants: = 3.76 mol; CO=1 mol Product 0s = 0.5 mol; Nz = 3.76 mol; CO; = 1 mol Al = (1 x 34.83 + 3.76 x 33.03 + 1 x 29.23)(298 — 373) = - 14119 J = (0.5 x 34.83 + 3.76 x 33.03 + 1 x $3.$9)(T - 298) = 195.20 T- 58169 where T is the adiabatic flame temperature, Using Eq. (3.55), we get 195.20 T ~ $8169 = 14119 + 283178 Solving this, we get the theoretical flame temperature as 1821 K. SUMMARY The general P-V-T behaviour of Huds, the physical significance of the triple point and the eritical point and the process of fusion, sublimation and vaporisation were discussed with the help of a PY diagram and a PT diagram for « pure fluid (Section 3.1). An equation of state is the functional relationship between pressure, volume, and temperature of the fluid. The most simple of such equations (PV = RT) is obeyed by ideal gases. The salient features of an ideal gas were described from microscopic as well as macroscopic points of view (Section 3.2). The heat and work involved in various processes with ideal gases, such as the constant volume process, the constant pressure process, the isothermal process, the adiabatic process, and the polytropic pracess were derived (Section 3.3). The changes in the internal energy (U) and the enthalpy (H) of an ideal gas area You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.P-V-T Behaviour and Heat Effects a] 3.13 Calculate the pressure developed by 1 kmol gaseous ammonia contained in a vessel of 0.6 m° capacity at a constant temperature of 473 K by the following methods: (a) Using the ideal gas equation (b) Using the van der Waals equation given that 4233 N mYmoF; b= 3.73 x 10-4 m'/mol 128 bar: Ty = 405.5 K 3.14 Determine the van der Waals constants and the molar volume of ethane at the critical point, given that the critical temperature and pressure are respectively 305.2 K and 49.4 bar, 3,18 Using the Redlich-Kwong equation calculate the molal volumes of saturated liquid and saturated vapour of methyl chloride at 333 K. The saturation pressure of methyl chloride at 333 K is 13.76 bar. The critical temperature and pressure are respectively 416.3 K and 66.8 bar (©) Using the Redlich-Kwong equation given that Pc 3:16 Using the virial equation calculate the molar volume and compressibility factor of isopropanol vapour at 473 K and 10 bar. The virial coefficients are: B= -388x 104 mmol; C= ~26 x 10-* mmol? 3:17 Determine the molar volume of gaseous methane at 300 K and 600 bar by the following methods; (@)_ Using the ideal gas equation (b) Using the van der Waals equation given that 4 = 0.2085 N fmol? b = 4.27 x 10° m'/mol (©) Using the Redlich-Kwong equation given that Te 318 An empirical equation PVE = C, where C is constant, is used wo relate P and V of any reversible process, Show that for an ideal gas this equation Teads to a4 RT, Ps wea |1-(2 oot R ‘Show that in the case of an isothermal process when A = 1, the above equation reduces to 4 weerrina 3:9 Heat of combustion of solid carbon and gaseous CO are respectively ~ 393,78 kl/mol and = 283.18 ki/mol, Determine the heat of formation of CO. 320 Using Hess's law evaluate the heat of formation of solid CaCOs, The following data are available74 A Textbook of Chemi Engineering Thermodynamics (b) C (3) + Os (g) > COs (2); AH y = 393.77 kd ©) CxO (9) + C05 (8) -% CHC, (8); AM = 178.15 8S 321 Calculate the standard heat of reaction for the following reaction: 2 FeSs(8) + 2 Os (g) + Fess (8) +4 803 8) ‘The standard heat of formation at 298 K are ~178.02 kI/mol for FeS3 (s), -822.71 ki/mot for FeO, (s) and ~297.10 k¥/mol for SO. (. 3.22 The standard heat of combustion of benzene at 298 K is ~ 3269.5 ki/mol when burnt completely to COs and liquid water. The standard heat of combustion of hydrogen to Tiguid water is ~286.04 kI/mol and that of earbon to earbon dioxide is ~393.78 k¥/mol Caleulate the standard heat of formation of liquid benzene, 298 K for th 3.23 The standard heat of reaction following reaction is 42.433 KJ, aH (g) + H30 (g) > C3HSOH (g) Calculate the heat of reaction at 400 K. The constants in the heat capacity equation Cp et Bs are as given below: (Cp is in Jmol K and T in K). @ B Y Hy 11.85 119.75 x 107 = 36.53 x 10% HO 30.38 9.62 x 109 +119 x 10% HOH 49.93 x 10% 166.39 x 109 324 The standard heat of combustion of graphite at 298 K is ~ 393.778 ki/mol. Determine the heat of combustion at $00 K. The heat capacities in J/mol K are: Carbon: 11.19 + 1.096 x 10°? 7 4894 10° e Ouyens 3462-4108 19 7 RIDE ss 3.28 Calculate the heat of combustion of methane at 800 K given that the heat of combustion ‘at 298 K is —802.861 ki/mol and the mean heat capacity in the temperature range from 208 K to 800 K are 41.868 Jmol K, 30.563 Jmol K, 41.449 Jmol K, and 34.332 J/mol K for methane, oxygen, CO, and water vapour respectively.P-V-T Behaviour and Heat Effects 75] 326 Ammonia is synthesised according to the following reaction: 3 $Nr+ 3H, NHy Aly =~ 4622241 The specific heats of the components are represented by Coe a Bre where Cp is in Imo! K and the constants a Band 7 are: BT N; 27.31 5.2335 x 10° = 4.1868 x 10° B 29.09 = 8374x104 +2.0139 « 10 i 25.48 36.89 x 10°* - 6.305 x 10° Express the heat of reaction as function of temperature, 3.27 Calculate the heat of the following gas-phase reaction 242 kd H+ 50:9 0, AHS, if the reactants are at 473 K and the product is at 993 K. The specific heats Cp = @+ BT + YF? Hol K may he evaluated using the data given below @ B r Hy 29.09 8.374 x 104 2.0139 x 10% 25.74 12.987 x 107 = 3.864 «10° 30.38 9.621 x 10 = 1185 x 104 3.28 Carbon monoxide (CO) at 1000 K is burned with air at 800 K in 90% excess air. The products of combustion Jeave the reaction chamber at 1250 K, Calculate the heat evolved in the reaction chamber per kmol of CO burned. The standard heat of reaction at 298 K is ~ 283.028 kI/mol CO. The mean specific heat applicable in the temperature range of this problem are 29.38, 49.91, 33.13, and 31.43 Imol K for CO, COs, Os, and Ny respectively, 3.29 Hydrochloric acid is produced from chlorine according 10 ‘The standard heats of formation at 298 K are ~241.82, ~92,307 ki/mol for water vapour and hydrochloric acid respectively. The reaction is to be carried out at $00 K with saturated steam at $00 K and chlorine gas at $00 K entering the reactor with a ratio of 3 mol steam per mol of ehlorine gas. Determine the amount of heat to be added or to be removed per kmol of acid obtained if the reaction goes to completion and the productsa You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.SECOND LAW OF THERMODYNAMICS 4.1 LIMITATIONS OF THE FIRST LAW OF THERMODYNAMICS ‘The first law of thermodynamics deals with energy changes involved in a process. But, it alone cannot answer many questions related to transformation of energy. The first law specifies only this: if energy is produced during a process, it must be compensated with a loss of an exactly cequall quantity, so that the total energy before and after the process are the same. It helps us to determine the energy changes involved in a process, but it cannot tell us whether a proposed change would actually occur or not. If it occurs, what is the direction of the change and what are the conditions of equilibrium under which the system undergoes no further change? The major limitation of the first law of thermodynamics is, therefore, its inability to deal with the direction of the process and the extent of change. Also, aecording 10 the first law, all forms. of energy are quantitatively equivalent and they are just additive terms in an energy balance. Tt fails to recognise the qualitative differences between various forms of energy. This difference is apparent when we attempt to convert heat into work by means of a heat engine. Before we embark fon the detailed study of the second law of thermodynamics, a discussion on these limitations is quite in order. 4A Direction of Change We have seen that the first law of thermodynamics deals with the amount of energy in different forms that are involved in various spontaneous processes, but it is not concerned with the ‘direction of change’. For example, when water on the top of a mountain runs to the bottom as. a stream or as a waterfall, the initial potential energy of water is converted 10 the kinetic energy and the first law of thermodynamics is satisfied, because, the total energy remains unchanged. It ‘would equally be satisfied in the reverse process in which the water flows upwards spontaneously. ‘The first law doesn’t suggest the impossibility of water flowing upwards spontancously. However, such an occurrence is contrary to our experience. Now, let us consider another example. When two bodies at different temperatures are brought into contact, heat energy flows from the body at high temperature to that at low temperature spontaneously. Heat energy will never flow from a lower temperature level to a higher temperature level without applying external work. According to the first law, the energy gained by the cold body should be equal to the energy lost by the hot body. Again, there is nothing in the first law that predicts that the transfer of heat must always be from the hot to the cold body. The first law ‘would be satisfied equally well if the transfer of energy took place in the reverse direction, but 7(80) A Textbook of Chemical Engineering Thermodynamics such a transfer never happens in nature, Similarly, we never observe a mixture of gases made up of wo oF more components spontaneously separating into its constituents, Though such a process is against our experience, it would not be inconsistent with the first law of thermodynamics as Jong as no net change in the total energy is involved. Thus, itis clear that apart from the first Jaw, but complementary to it, there should be some principle to deal with the spontaneous processes and their direction ‘The inadequacy of the first law of thermodynamics 10 explain our general experience with spontaneous processes or tendency 10 change led to the development of the second law of thermodynamics, which deals with the direction of change. With the help of the tools provided by the second law, we can find answers to many problems that are not answered by the first law. For a chemical reaction occurring from a given initial state of reactants to a given final state of products, the first law can be utilised to estimate the heat of reaction and the effect of temperature and pressure on it, But, will the reaction proceed spontaneously’? What is the equilibrium point ‘at which no further change occurs? How is the equilibrium affected by the operating conditions? ‘What is the maximum work available from a process? What is the minimum work required to carry out a process? What is the maximum efficiency with which a process could be carried out? Such questions are answered by the second law of thermodynamics, usually in combination with the First law. 4.1.2 Qualitative Difference between Heat and Work Another limitation of the first law of thermodynamics is that it does not take into account the in quality between heat and work. When we treat heat and work as additive terms in an energy balance, we are in fact ignoring the intrinsic difference between them. It is true that, in the application of the first law this difference is not going to affect our calculations. However when we consider converting heat energy to other forms of energy, the qualitative difference between heat and work would be obvious. It is possible to convert one form of work to another (such as electrical 10 mechanical) with almost 100 per cent efficieney, provided, the irreversiilities in the apparatus are eliminated. But the efficiency of converting energy transferred to a system as heat into any of the forms of work is limited to very low values. This leads us to the conclusion that heat is a less versatile or more degraded form of energy compared to the other forms of energy oof work can be terined energy of a higher quality than heat. During the conversion of heat into ‘work, a portion of the energy becomes unavailable, that is, not capable of being transformed into useful form, The difference between the quality of heat and other forms of energy are accounted for in the second law of thermodynamics. When we say that heat flows always from a higher to a lower temperature we are assigning a characteristic quality as well as quantity to heat, the quality being represented by temperature. We know that the efficiency of a thermal power plant increases as the temperature of the steam in the boiler increases. In the transformation of heat to work, the inerease in the efficiency that results from the increase in the temperature of the source clearly establishes the connection between the temperature and the quality of heat. differene 4.2 GENERAL STATEMENTS OF THE SECOND LAW OF THERMODYNAMICS The second law of thermodynamics is just the generalisation of our experiences with spontaneous processes and can be stated in a number of way:Second Law of Thermodynamics [ar] 1. Heat cannot by itself pass from a cold to a hot body. All spontaneous processes are, to some extent, irreversible and are accompanied by a degradation of energy. 3. Every system, when left co itself, will on the average, change toward a system of maximum probability, A. Kelvin-Planck statement, tis impossible to construct an engine that, operating continuously {in a cycle), will produce no effect other than the transfer of heat from a single thermal reservoir at a uniform temperature and the performance of an equal amount of work, This statement implies that at least 1wo thermal reservoirs of different temperatures are necessary for a heat engine to operate. This is because only part of the heat transferred to the engine from a high temperature reservoir is converted to work; the rest is rejected to a low temperature reservoir. Further, the statement implies that no heat engine can have 100% efficiency because heat cannot be completely converted to work. The word ‘continuous’ in the Kelvin-Planck statement has an important implication, Consider the isothermal ‘expansion of an ideal gas. The change in internal energy, AU, is zero in this process. This ‘means that the heat absorbed by the gas is completely converted to work. Though it may appear to contradict the second law, in fact, it is not so. What the second law requires is that there should be no change in the system or in the surroundings other than the complete conversion of heat into work. Here, the pressure of the gas has decreased and the process cannot be carried out continuously. The pressure of the gas would soon hecome equal to that of the surroundings, and further expansion would be impossible. The continuous conversion of heat to work is possible only in a cyclic process. But, in the cyclic process, energy from the surroundings is utilised in the form of work, in order to compress the gas back to ils original pressure, 5. Clausius staiement. It is impossible to construct a heat pump that, operating continuously, will produce no effect other than the wransfer of heat from a lower temperature body to a higher temperature one. In other words, any process, which consists solely in the transfer of heat from one temperature to a higher one, is impossible. It means that energy in the form of work must be supplied to the heat pump in order to transfer heat from a cold body to a hot body. Therefore, the coefficient of performance of a heat pump can never be infinity. 4.2.1. The Equivalence of the Kelvin and Clausius Statements All the statements of the second law are equivalent and mean the same thing. Any device that violates any one of these statements will violate all other statements. Figure 4,1 shows an engini which violates Kelvin-Planck statement by absorbing heat from a single thermal reservoir and producing an equivalent amount of work. The work output of this engine (W = Q,) is used to drive heat pump which transfers an amount of heat Qz from a low temperature reservoir and an amount (Q1+ 2) to a high temperature reservoir. The combined system shown by the dotied lines in the figure then act as heat pump which transfers an amount of heat Qs from a lower temperature to a higher temperature reservoir without using any external work. This is a violation of Clausius statement Now consider a heat pump, which violates the Clausius statement, by absorbing heat Qs from a low temperature reservoir and transferring it to high temperature reservoir (Fig, 4.2). Let a heat(32) A Textbook of Chemical Engineering Thermodynamics High-tempermure reservoir Combined system Low-temperature reservoir AA heat engine that violates the Kelvin-Planck, statement. High-temperature reservoir a ‘ 7 Sombie system Low-temperature reservoir Fig. 4.2 A heat pump that violates the Clausius statement. engine work between these two reservoirs by absorbing heat Q, (Qi > Q:) delivering work W (W = Q; ~ Qz) and rejecting heat Q; to the low temperature reservoir. Since this process does not affect the low-temperature reservoir, the net effect is a heat engine operating with a single reservoir absorbing heat Q;— Qs and converting it completely to work. This is a violation of the Kelvin-Planck statement 4.3 ENTROPY 4.3.1 Why the Concept of Entropy? ‘The second law of thermodynamics states that all spontaneous processes are, to some extent,Second Law of Thermodynamics [a3] irreversible and are accompanied by a degradation of energy. It also means that itis impossible for any self-acting machine to transfer energy from a given state to a higher state of availability ‘To make these statements quantitative there is required some function that always changes in a certain way during a spontaneous process and therefore, will characterise such a change. Internal energy was defined t0 give quantitative significance to the first law. Internal energy does not change in any characteristic way in a spontaneous process, and it does not help in any way in the development of the second law. The function that is fundamental in the development of the second law is entropy, which means transformability (change) in Greek, introduced by Clausius in 1851. Later in this chapter, we will show that the second law of thermodynamics necessitates, that all spontaneous processes result in an increase in the entropy and no process is possible that results in a decrease in entropy. Consider an imaginary process for gas separation as illustrated in Fig. 4.3. Assuming that the ‘gases behave ideally, the change in the intemal energy, AU = 0. On the basis of the first law, the process is not an impossible one. With the aid of the entropy function it can readily be shown that the imagined process is impossible, because, it would involve a net decrease in entropy of the system with no corresponding increase in the entropy of the surroundings, Oxygen at 1 bar and 300 K Air at 1.5 bar and 300 K ~ Air separator a Nitrogen at 1 bar and 300 K Fig. 4.3 A process that is permitted by the first law, but that viol 5 the second law, We have seen that although there is an exact quantitative equivalence among the different forms of energy, there is a marked difference in the availability of these forms for useful work. Heat represents the least ‘available’ form of energy and transformation of other forms into heat represents a degradation of energy. Entropy is the thermodynamic property, which serves as a measure of the unavailability or degradation of energy. An increase in unavailability of the total energy of a system is quantitatively expressed by a corresponding increase in its entropy. Entropy, being an intrinsic property of matter, is not affected by the extemal position of the body or its motion relative to other bodies. The entropy of unit mass of water atthe top of the mountain is equal to the entropy of the same amount of water at the bottom of the falls, if the temperature and pressure are the same. Similarly, the entropy of unit mass of water in the flowing stream will be equal to the entropy of water in a stagnant pool, provided that the conditions such as the temperature and pressure are the same in both the cases, The entropy of a system is affected only by the nature of matter under consideration and by the state in which it exists, 4.3.2. Entropy and Heat [As noted above, the entropy is a measure of the unavailability of the internal energy. Among the various forms, heat is the least available form of energy. Whenever a certain form of energy gets transformed to heat the total energy gets degraded with a corresponding increase in the entropy of the system. Consider 1 kg of water at the top of mountain of height about 426.8 m. At this position, water possesses a potential energy of nearly 4.187 kJ. When the water falls and strikes the river at the bottom, all its potential energy gets converted to thermal energy with a consequenta You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.Second Law of Thermodynamics [39] The work done during the isothermal compression CD is given by Wop = RT, In 2 ah uy Substituting Eqs. (4.10) and (4.11) into Eq, (4.9), we get 4.12) Equations (4.10) and (4.12) lead the following equation for the efficiency of the engine: = Meas = RT In(Py Py) + RT, IMPLIES) _ 4 , Te'0PI 2) =O RT, In(P,/P,) Tn?) ois) ir amas pce RC GRAD, aption an piesa Lene a fos ao ee 2.(% for process DA (aly) Tt \Po 5 (eye Fn F) orproces 8c as) ZR Comparing Hao. (414) and (4.15), wo ow tat Paolo ane 16) Substituting Eq. (4.16) into Eq. (4.13), we get 4.17) By the first law of thermodynamies Way = Qj ~ Qs. Therefore, Eq. (4.17) can be written as o- Q (4.18) @ @ Comparison of Eq. (4.18) with Eq, (45) shows thatthe ideal gas temperature and the absolste thermodynamic temperatre are identical90. A -xibook of Chemical Engineering Thermodynamics EXAMPLE 4.1 A heat engine operates between a heat source at 700 K and a heat sink at 300 K. What is the maximum efficieney of the engine? Solution The efficiency of a Carnot engine operating between «wo temperature levels 7) and Tz is given by Eq, (4.17). This is the maximum efficiency that can be expected of any heat engine. Therefore, the theoretical efficiency of the given engine is 700 - 300 037 700 EXAMPLE 4.2 tis required to freeze | kg water at 273 K by means of a refrigeration machine which operates in the surroundings at 300 K. The latent heat of fusion of ice at 273 K is 334.11 ki/kg. Determine: {@) The minimum amount of work required (b) The heat given up to the surroundings. Solution The work required will be minimum for an ideal Camot machine acting as a refrigerator. The coefficient of performance (COP) of sueh a machine is given by the relation cop= 2 = —h Wah 4.19) Here, Qais the heat absorbed at a temperature T>, and 7, is the temperature of the surroundings to which heat is given up. For freezing 1 kg water, the heat to be removed is 334.11 KI, ic. Or = 334.11 KI. (a) From Eq. (4.19), w= QE=T) _ 554.1) 300-273 273 (b) Since W = Q, ~ @, 2. EXAMPLE 4.3 new engine is claimed to be having a power output of 4.5 hp while receiving a heat input of 6.25 KW and working between the source and sink temperature limits of 1000 K and $00 K. Determine the efficiency of the proposed engine. Is the claim for the engine admissible? 33.04 + 334,11 = 367.15 kd Wear Solution ‘The work output of the proposed engine is 4.5 745.7. = 3355.65 W and the heat input is 6250 W. The efficiency of the proposed engine is, therefor 3355,65/6250 = 0.537 ‘The maximum efficiency of an engine working between the temperature limits 1000 K and 500 K is the Carnot efficiency. Thus, the maximum efficiency is 1, _ 1000 - 500 7 1000 0.50Second Law of Thermodynamics [st] No engine can have an efficiency greater than this value. Hence the claim of the proposed engine is impossible, 4.5 ENTROPY—A STATE FUNCTION Equation (4.18) can be rearranged as aS a 1, where Q; is the heat absorbed and Qs is the heat rejected by the system. The heat absorbed by the system is positive and heat rejected is negative as per the sign convention we have adopted so that the above equation should be written as %__& ae 4.20) Bao 3 ne 42 Equation (4.21) means that the sum of the quantities Q,/T, and Q,/T, for a reversible heat engine is zer0. Any reversible cyclic operation like the one represented on the P-V diagram in Fig. 4.6, may be regarded as made up of a large number of imaginary Camot cycles and for each such cycle ‘we can write equation similar to Eq. (4.21) as 4.22) where dQ} and dQ: are the heat absorbed and heat rejected respes imaginary cycle ely during one such an Pressure Volume Fig. 4.6 A reversible cycle divided into a number of Carnot’s cycles,92 A -xibook of Chemical Engineering Thermodynamics Combining all such equations that are written for the separate Camot cycles into which the original reversible cycle is divided, we get 4 § Seo 423) T where the subscript R refers to the reversible process and the eyclic integral limits the equation to the eyclic operation. We have defined entropy change in a process by Eq, (4.1). Substituting Eq, (4.1) into Eq. (4.23) we see that § = Wig aay where 8 isthe enopy of the sytem, We have chanctrsed the themodymamic property of a ‘pnom as quay thot undergoes no net change in eye operon, Eguaon (420) meant thr the entropy change A for he cyclin operation fe equal to eos oi show, eiropy $a Ckfined by Eq: 1) ia thermodynanie propery ofthe system, I reveals an ineresng fact Where te heat tansfered ina proces 18 path uncon, the rao of the hee trangered tothe Sempertuce dt Which it ranged tsa sate function 4.6 CALCULATION OF ENTROPY CHANGES ‘The entropy change as defined by Eq. (4.1), accompanying a process is applicable for a reversible process. In practice, processes are never carried out reversibly. Entropy being a state funetion depends only on the end states. The entropy change in an irreversible process occurring between any two states would be the same as the entropy change in a reversible process occurring between them, the latter being evaluated by Eq. (4.1). Thus, the entropy change in any irreversible process can be evaluated by devising an imaginary reversible process for accomplishing the same change and calculating the entropy change in the latter. If the process involves only the direct transfer of heat or the degradation of higher forms of energy into heat, the restriction of reversibility in Eq. (4.1) may be ignored. Thus, entropy change due to the addition of heat can always be calculated by Eq. (4.1), whether the transfer is accomplished reversibly or irreversibly. Similarly, for processes involving the changes in the relative position or movements of matter (as in the case of a falling object) the heat added, even if the process is highly irreversible, measures the entropy change. However, if a process is irreversible because of a finite difference in another driving force, such as pressure, calculation of entropy change is done by devising a reversible process for accomplishing the change. Thus, we see that in the evaluation of entropy changes, the reversibility restriction is 10 be strictly followed only for processes involving changes in the intrinsic state of the matter. 4.6.1. Phase Change ‘The entropy change in phase transitions like fusion, vaporisation, or transition from one crystalline form to another can be evaluated from the values of the latent heat of phase change and the temperature at which the change is carried out, The phase changes can be treated as changesSecond Law of Thermodynamics [93] ‘occurring reversibly at constant temperature. For example, the entropy of vaporisation ASy is found out as (4.25) EXAMPLE 44 Calculate the entropy of evaporation of dry saturated steam at $00 kPa, Data: From the steam tables, latent heat of vaporisation, AH, = 2106 ki/kg: Saturation temperature of steam = 425 K. Solution By Eg, (4.25), entropy change accompanying vaporisation is ASy = 2106/425 = 4.96 kitkg K 4.6.2 Processes involving Ideal Gases Fora differential change in the thermodynamic state ofa closed system, the first law of thermodynamics [Eg. (2.5)] can be written as dg=du+dw ‘When the process is reversible and the work involved is only work of expansion (P dV), the above equation can be modified as ao, Since this infinitesimal change in the state of the system can be assumed to occur at constant temperature T, the entropy ehange by Eq. (4.1) is au + Pav ds= (4.26) For an ideal gas, dU = Cy dP and P = RIV. dT + RT AVIV) _¢. aT, gaV. T Assuming that Cy is independent of temperature, this equation can be integrated for a finite change from state 1 t0 state 2 giving for one mole of an ideal gas, 427) where the suffixes | and 2 indicate the properties of the gas at state 1 and state 2 respectively. Equation (4.27) can be used for the evaluation of entropy change accompanying the change in states of ideal gases. It ean be put in another form also. We know that for ideal gases, -R (4.28) and Ey i (4.29)4 A -xibook of Chemical Engineering Thermodynamics Substituting Eqs. (4.28) and (4.29) into Eg. (4.27), we obtain the following: AS = Cpln 4.30) 431) For constant pressure process, we have b AS =Cpin 2 Wn 4.32) For an isothermal process, we obtain AS=Rin 4.33) ‘Though the above equations are derived on the premise that the processes are reversible, they can be used for irreversible processes occurring between the same terminal conditions as well. This is because the change in entropy depends only on the end states and not on the history of the system. EXAMPLE 48 Determine the change in entropy when 2 kg of a gas at 277 K is heated at constant volume to a temperature of 368 K. Take the specific heat at constant volume = 142 ki/kg K. Solution Entropy change accompanying a constant volume process is given by Eq. (4.31), For m= 2 kg, 368 .0(1.42) In 55> AS = mCy In = 8067 KI EXAMPLE 46 Calculate the entropy change when 1 kmol of an ideal gas at 300 K and 10 bar expands through a throttle to a pressure of 1 bar, both pressures being maintained constant during the process by suitable means. Solution During throttling enthalpy is unchanged. For an ideal gas enthalpy being a function of temperature alone, the temperature remains unchanged during the process. Therefore, entropy change accompanying the process can be computed by Eq. (4.33). ENAMPLE 4.7 What is the change in entropy when 1 kmol of an ideal gas at 335 K and 10 bar is expanded irreversibly to 300 K and 1 bar? Cp= 29.3 ki/kmol K.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.Second Law of Thermodynamics icxal EXAMPLE 4.11 Calculate the entropy change for the following gas phase reaction occurring at I bar and 298 K, 1 CO#50:= COs AM =~ 28318 x 10° J/mol ‘The absolute entropies of CO, oxygen and COs are respectively 198 J/mol K, 205.2 kifkmol K and 213.8 Wkmol K. Can you calculate the entropy change as the ratio of heat of reaction to the temperature of the reaction? Why? Solution Refer Eq, (4.36), The reactants are CO and oxygen. The product is Ct s 198 + 0.5 x 205.2 = 300.6 VK 213.8 ~ 300.6 = ~ 86.8 WK 213.8 UK, As Since the reaction is highly irreversible, entropy change cannot be calculated as the ratio of heat of reaction to the temperature, (AH _ 28318 x 10° (7 28 Ass 950.27 UK ‘The heat of reaction (~ AH) is the heat liberated when the reaction occurred irreversibly. If the reaction were carried out reversibly, for example, in an electrolytic cell with the generation of electric energy, the heat liberated would he (~ TAS). Therefore, the difference between these (wo represents the heat loss hecause of the irreversible nature of the process, or the heat that could have been utilised for the production of useful work like electrical energy. Thus the energy available for useful work is 2.8318 x 10° — 298 x 86.8 2.57314 x 10°F 4.7 CLAUSIUS INEQUALITY ‘The Carnot principle states that a reversible heat engine is more efficient than an irreversible engine. The efficiency of a reversible engine is given by Eq. (4.17) Now consider an irreversible engine operating between the same thermal reservoirs. Let dQ; be the heat absorbed and dQ be the heat rejected by the engine, The efficiency of the engine is 40-40, _, 40, dQ, dQ, 437) ‘Then, by Camot principle (4.38)which means ‘Adopting the sign convention that the heat rejected dQ is negative, the preceding relation gives 40, , 10, <4 T (4.39) An irreversible cyclic operation can be divided into a number of heat engine cycles involving infinitesimally small heat interactions, as we have done in Fig. 4.6 for the case of a reversible cyclic operation. For each such eycle, itis possible to write equations analogous to Eq. (4.39) so that the net result would be do < 4.40) § <0 where T is the temperature of the thermal reservoir. Combining Eq, (4.23) for the reversible eye! operation with Eg, (4.40) for the irreversible process, we get aly which is known as Clausius inequality. It states that in a eyelic operation, the sum of the dQt T terms around a complete cyele is less than or equal to zero depending on whether the process is irreversible or reversible. EXAMPLE 4,12 Using Clausius inequality show that the change in entropy in a process is related to the heat interaction as ‘where the greater than sign refers to an irreversible process and equal to sign refers to a reversible process. Solution Consider a reversible process between states A and B as illustrated in the P-V diagram (Fig. 4.7). For this process, the change in entropy by Eq. (4.1) is dQ MSay =f 42) i? aaSecond Law of Thermodynamics [99] Reversible process Pressure Irreversible process Volume Fig. 4.7 P-V diagram for the process in Example 4.12. where dQ is the heat change involved in this step. Assume that the system is brought back 10 the initial condition along an irreversible path BA. The system has undergone a complete cyel of operations. Entropy being a state property, net change in entropy is zero forthe cycle. That is Sur Su =0 Since the cycle as a whole is ireversble, Eq. (4.41) gives dQ dQ as 7 ma T “° Using Eq, (4.42) in the above inequality do aur f Po This inequality can be written in another form dQ ~ASm + f <0 (a3) where ASpa represents the entropy change along the reversible path from B to A. Equation (4.43) ‘ean be rewritten as asa > f & ‘The entropy change for the processes occurring along a reversible path and an irreversible path Detween the same end states A and B should be the same. The leftchand side of the precedinga You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.02 -xibook of Chemical Engineering Thermodynamics (AShuei 2 0 (4.49) Equations (4.46) and (4.49) are the general mathematical statements of second law of thermodynamics. ‘These statements apply to the total change in entropy: in an irreversible process, a decrease in ‘entropy may occur either in the system or in the surroundings. These statements require only that, the sum of the entropy changes of the system and the surroundings together be positive in an irreversible process like the isothermal expansion of a gas. Ifthe same expansion were carried out reversibly, the inetease in the entropy of the gas will be compensated by a decrease in the entropy ‘of the surroundings that results because of the withdrawal of heat. If this heat exchange also were accomplished reversibly, the net change in entropy would be zero. Equation (4.49) is also known as the principle of increase in entropy: ‘The principle of increase in entropy with reference to an isolated system means that the only processes that can occur in an isolated system are those that have an increase in entropy associated with them. The universe is a perfect example of an isolated system and all naturally ‘occurring processes in the universe are accompanied by an increase in entropy and are irreversible. Hence we can say that the entropy of the universe goes on increasing. The statements for the first and second laws of thermodynamics can now be combined: The energy of the universe is conserved whereas the entropy is increasing. EXAMPLE 4.13 One kilogram of superheated steam at 1.5 MPa and $23 K (H = 2923.5 ki/kg, S = 6.71 ki/kg K) is contained in a piston-eylinder assembly. The unit is kept at ambient conditions of 300 K and the steam condenses to saturated liquid (H = 845 kWkp, S= 2.32 KWdkg K) at constant pressure, Caleulate the change in entropy and check whether the process is reversible oor not Solution The change in entropy of steam is the difference between the entropy of the ‘condensate and entropy of superheated steam. That is, = 6.71 = —4.39 kitke K Change in entropy of steam = At constant pressure, the change in enthalpy is equal to the heat supplied. Thus, the heat given ‘out by steam during condensation, Q = —AH = 2923.5 ~ 845 = 2078.5 kimk Change in entropy of the surroundings is @ _ 20785 2. UIBS _ 693 = ATES = 693K Therefore (Shoat = 254 KM Since (AS) i8 positive, the process is irreversible. EXAMPLE 4.14 Two compartments each of | m? capacity are connected by a valve and insulated from the surroundings and from each other. One compartment contains saturated steam at 683.6 kPa and the other contains steam at the same temperature but at a pressure of 101.3 kPa. The valve is opened and the pressure is allowed to equalise. Determine the change in entropy of the system consisting of the two vessels. Comment on the irreversibility of the processSecond Law of Thermodynamics 103 Solution From steam tables, the enthalpy, entropy, specific volume and internal energy of saturated steam at 683.6 KPa (T, = 437.2 K) are 2761 KWKg, 6.7133 kWkg K, 278.9 > 10°? m kg and 2570.4 kilkg respectively. For superheated steam at 101.3 KPa and 437.2 K, these values are 2804 ki/kg, 7.6712 Kifky K, 1976.2 m'ky and 2603.3 kg respectively Mass of saturated steam: 1.0/(278.9 x 10) = 3.5855 ky. Mass of superheated steam: 1,04(1976.2 x 105) 0.5060 ke Mass of the system: 3.5855 + 0.5060 = 4.0915 ke Specific volume of the system: 2.0/4.0915 = 0.4888 meg Since no heat exchange and work interaction between the system and the surroundings occur uring the mixing process, according to the first law of thermodynamics, the internal energy after ‘mixing remains the same as that before mixing. The internal energy of saturated steam is 2570.4 x 3.5855 = 9216.2 KI ‘The internal energy of superheated steam is 2603.3 x 0.5060 = 1317.3 KI Therefore, the specific internal energy of the system is (0216.2 + 1317.3)/4.0015 = 25745 kifkg ‘The internal energy and specific volume of the system after mixing are now known. They are 2574.5 ki/kg and V= 0.4888 m°vkg. These determine the state of the system. By interpolation of the data from steam tables we get the pressure = 400 kPa and temperature = 437 K and the entropy of the system = 6.9992 kifkg K. Initial entropy (6.7133 X 3.5855 + 7.6712 x 0.5060) = 27.9522 KK Final entropy = 6.9992 x 40915 = 28.6372 ki/K Change in entropy = 0.6880 KI/K: [As the surroundings are unaffected, the above value represents the total entropy change. Since it is positive, the process is ineversible, EXAMPLE 4.15 Two perfectly insulated tanks each of capacity 1 m* are connected by means ‘of a small pipeline fitted with a valve. The first tank contains an ideal gas at 300 K and 200 kPa and the second one is completely evacuated. The valve is opened and the pressure and temperature are equalised. Determine the change in total entropy. Solution Using the ideal gas equation, the number of moles of the gas is determined,104 -xibook of Chemical Engineering Thermodynamics PV 200x1 Quantity of gas = PY = 2001 yofe RT 8.314 x 300 (0802 kmol ‘The system, which, in this ease, is the gas contained in the vessels, exchanges no heat and work ‘with the surroundings. By the first law AU =0. The internal energy of an ideal gas depends only ‘on temperature and therefore temperature after mixing is the same as that before mixing. Thus wwe have, Final conditions: T= 300 K, V= 2m and P Initial conditions: T= 300K, V= 1m! and P Equation (4.33) can be used to evaluate the entropy change. 2 AS = R In 7 = 5.7628 kivkmol K = 0.0802 x 5.7628 = 0.4622 KI/K Entropy of the surroundings does not change. Hence, the change in total entropy = 0.4622 KI/K. EXAMPLE 4.16 Oil at 500 K is to be cooled at a rate of 5000 kg/h in a counter-current exchanger using cold water available at 295 K. A temperature approach of 10 K is to be ‘maintained at both ends of the exchanger. The specific heats of oil and water are respectively 3.2 and 4.2 ki/kg K. Determine the total entropy change in the process. Solution Assume that the oil is cooled to the minimum permissible temperature. Then the inlet and exit temperature of the oil are $00 K and 305 K. The inlet and exit temperature of the water are 295 K and 490 K. The mass flow rate m of water can be determined by an enthalpy balance, m x 4.2 x (490 ~ 295) = 5000 x 3.2 x (500 ~ 305) Solving this, we get m = 3809.5 kg/h. Entropy change of oil and water can be calculated by where Ty and T, are the final and the initial temperature of the fluid, respectively, 305 4 = 5000 x 32 x In 32> = (AS)oy = 5000 on 79087 KI/K (5 ue = 8085 42 xin BY uss ‘Total entropy change = 8118.8 ~ 7908.7 = 210.1 kKSecond Law of Thermodynamics 105 4.9 ENTROPY AND IRREVERSIBILITY ‘The total increase in entropy associated with an actual process is a measure of the loss in capacity of the system and surroundings as a whole to do work. In other words, the increase in entropy accompanying a spontaneous process is a measure of lost work. Consider an irreversible process in which a quantity of heat Q is transferred from a souree ata temperature T; to a sink at a lower temperature T3. The change in total entropy in this process is given by Bq. (4.48). Now consider a reversible heat engine operating between the same thermal reservoirs receiving the same quantity of heat Q. The efficiency of such an engine is given by Eq. (4.17) ‘The work output of the engine can be calculated as the product of the efficiency and the heat input. (4.50) ‘This is the work which would have resulted had the heat transfer process been reversible, but which was lost because of the irreversible nature of the process. Equation (4,50) can be modified i= w-79l-h QO Fz 51) Equation (4.51) can be combined with Eq. (4.48) to give Wow = FAAS) (452) Equation (4.52) gives a physical meaning to the total entropy change in an irreversible process. ‘The product of total entropy change and the temperature of the heat sink gives the quantity oF heat that is wasted or degraded in an irreversible process. A reversible engine which receives heat Q; from the reservoir at temperature T, would perform some work rejecting a part of it, say Q>, to a heat sink at temperature 73, The heat rejected in the ease of an irreversible engine which receives the same amount of heat would be greater by an amount equal to T:(AS)a1- Thus TAAS)oui represents heat taken in at a higher temperature that would have been available for doing work had the process been reversible, but that was lost because of the irreversibility of the actual process ‘Though Eq. (4,52) is developed for a heat transfer process, it can be shown that it is applicable to any process, We can generalise the equation into the following form Won = ToAShow (4.53)106 A -xibook of Chemical Engineering Thermodynamics 7, is the temperature of the surroundings. In practice, itis approximately equal to the temperature of the atmosphere. The lower the value of 7), the lesser the work loss due to irreversibility of the process. But, the lowest practicable temperature is that of the atmosphere. To maintain the temperature of a heat sink below that of the atmosph hhe more than that is gained by lowering Tp, ., work is needed, and this work would EXAMPLE 4.17 Evaluate the loss in capacity for doing work when the steel casting in Example 4.9 is quenched in oil Solution Refer Example 4.9. The change in entropy of the casting is 26.25 KI/K, ‘The change in entropy of the oil is 43.90 NK, ‘The total entropy change is (AS) gat = AS) + AS) = 17.65 RIK ‘The loss in capacity for doing work is TyAS = 275 x 17.65 = 4853.75 KI This is the net work, which would have been accomplished if all the changes resulting from the process had been catried out reversibly. EXAMPLE 4.18 Hydrocarbon oil is to be cooled from 425 K to 340 K at a rate of S000 kgfh in 4 parallel flow heat exchanger. Cooling water at a rate of 10,000 kg/h at 295 K is available. The ‘mean specific heats of the oil and water are respectively 2.5 kikg K and 4.2 kifkg K. (a) Determine the total change in entropy. Is the process reversible? (b) If a reversible Carnot engine is 1 be operated receiving the heat from the oil and rejecting the heat to the surroundings at 295 K, how much work would be available? Solution ‘The exit temperature of water is obtained by an energy balance. Assuming no heat loss, the energy balance gives 5000 x 2.5 x (425 ~ 340) 10000 x 4.2 x (~ 295) where T is the exit temperature of cooling water. Solving this, we get T= 320.3 K. (a) The change in entropy of oil: 340. 5000 x 25 x In 0. 5000 x 25 «In 3 27893 KK Change in entropy of water: 10000 x 4.2 xn 3208 = 34580 4K 295Second Law of Thermodynamics 107 Total entropy change is (AS)ou + (AS)oaue = 3455.9 - 2789.3 = 666.6 KIK Since this is positive, the process is irreversible (b) The heat given out by the oil on cooling, Q = S000 x 2.5 x (425 ~ 340) = 1.0625 x 10" kus ‘The heat rejected Q; to the surroundings at Ty by the Carnot engine is given by TQM) =~ TAS where AS is the change in entropy of the oil, The work ouput of the engine would be Q ~ Qs = 1.0625 x 10° — 295 x 2780.3 = 2.39657 x 10° KI 4.40 STATISTICAL EXPLANATION FOR ENTROPY ‘To understand the physical meaning of entropy. the relationship between entropy and probability should be made clear. All spontaneous processes arc in the direction of maximum probability and, ‘as we have shown in the preceding sections, they are accompanied by an increase in entropy. For example, consider the spontaneous process of mixing of the two pure gases A and B in a container. ‘The pure gases, which were initially separated by a membrane, are allowed to mix together. The most probable state in which the system exists is the ‘mixed-up’ state, and the chanees for one part of the vessel being occupied by pure A and the other part by pure B are very remote. This ‘concept may be illustrated by a large number of white and black balls shaken together in a box. ‘The most probable average arrangement is a uniform distribution of black and white balls and 4 compartment of the box being occupied by balls of only one colour is hardly observed. We see that the most probable state in which a system can exist is that having the least orderly ‘arrangement, That is, in the most probable state of the system the molecules are distributed with greatest randomness. The second law of thermodynamics in its most general form can be stated thus: every system, which is left 0 itself, will, on the average, change towards a condition of maximum probability. All spontaneous processes occur in the direction from order to disorder and chaos, and an inerease in entropy is associated with all these processes. Thus entropy may be looked upon a measure of randomness which is a minimum in systems with an orderly arrangement, Consider, for example, the diffusion of one gas into another. The molecules of the gases, which were initially separated, have mixed in a random manner. The spontaneous conduction of heat along a metallic bar results in a random distribution of the kinetic energy of the molecules. The rejection of heat from a system though decreases the disorder of the molecules, an equivalent or greater amount of disorder results in the environment. It is therefore reasonable to postulate a relationship between the entropy of the system and the randomness or degree of disorder in the given state.(08) A Textbook of Chemical Engineering Thermodynamics The concept of entropy as a measure of randomness is also helpful in predicting qualitatively whether a proposed process is accompanied by an increase or decrease in entropy, from a consideration of randomness or disorder in the initial and final states. Similarly, knowledge of the entropy change often provides information concerning structural changes accompanying a given process. To illustrate this, consider a substance undergoing a change of phase from solid to liquid. The process involves an increase in entropy as well as an increase of disorder. In general, the greater the increase of disorder accompanying a process, the greater is the increase in entropy. Boltzmann (1896) put forward the statistical definition of entropy by the following relation. king 454) In this equation, k is the Boltzmann constant and the quantity @ is the number of different ways in which the energy of the system can be achieved by rearranging the atoms or molecules among their available states 4.11 THIRD LAW OF THERMODYNAMICS, We have seen in the previous section that the more completely a system is shuffled the greater is its entropy. Entropy is a measure of the randomness of molecular arrangement of a system. An orderly or unmixed configuration results in low entropy. It is natural therefore, to expect a substance to have zero entropy when it reaches a state in which all randomness have disappeared. A perfect erystalline substance at the absolute zero of temperature would meet this requirement and should have zero entropy. Using the experimental data on the heat capacity of perfect crystalline substances at very low temperatures their entropy at 0 K was calculated and it was shown that they all have same entropy values at this temperature. These observations lead 10 the postulate of the third law of thermodynamics: The absolute entropy is zero for a perfect crystalline substance at absolute zero of temperatures. In comparison with internal energy and enthalpy, which are caleulated relative to an arbitrary reference state, entropy is a reference property and is absolute, as are pressure, volume and temperature. Third law of thermodynamics can be utilised to ealeulate the absolute entropy of substances at a given temperature by assigning the value zero for entropy of the crystalline form of the substance at absolute zero. This is done by measuring the heat capacity at different temperatures and the Tatent heats of phase transition that the substance must have undergone to arrive at the present state from the initial siate of absolute zero of temperature. For example, Tet the melting point of the substance be T,and the boiling point be T,. The entropy at T, where T is above the boiling point may be evaluated as T, CpsdT | AH, T, CodT | MHy T CpgdT sia [ot Soot, le Ea le pr Et 455) be th, aa th, a where Crs Cp, and Cpe are the spcifc heats of sli, liquid and gas respectively, and Ad and [ify are ihe leet heats of fasion and vaporisation respectively, The main ificul in using the above eauaton is with regards 1o the measurement of heal eapaciy at very low femperatres, EXAMPLE 4.19 It is known that the molar heat capacity of a substance at low temperatures can be approximated by the relation Cp= a7°, where a is a constant. Determine the molar entropy fof a metal at 10 K if the molar heat capacity at this temperature is 0.45 Smal K.Second Law of Thermodynamics 109 Solution ‘The entropy of the solid at 10 K is evaluated using the first integral in Eg. (4.55) PS 2° ad rT 3 fot af ant elen At temperature T, Cp= aT". Therefore, s 3 = 0.45/3 = 0.15 Hol K EXAMPLE 4.20 Calculate the absolute entropy of water vapour at 473 K and 101.3 kPa above 273 K base temperature, Compare this with the value reported in steam tables (S.= 7.829 kW/ke K). ‘The average heat capacity of water = 4.2 kW/kg K and that of water vapour between 373 K and 473 K = 1.9 Kikg K. The latent heat of vaporisation at 373 K = 2257 kW/kg. Solution Equation (4.55) is reduced to the following form for the present purpose. wh rg BA 6 19 5219 7 gost s 101 $= 7.813 kifkg K and it compares favourably with the value reported in the steam tables: 7.829 kiikg K. SUMMARY ‘The first law of thermodynamics is concerned with the amount of energy in different forms that are involved in various spontaneous processes. But, it fails 10 explain the direction and extent of such processes. Though heat ean be treated as a form of energy there is a marked qualitative difference between heat and other forms of energy. Because of these inadequacies of the first law in explaining the naturally occurring processes, the second law of thermodynamics was proposed, which can be stated in a number of ways. To give a mathematical expression for the second law, the concept of entropy was introduced, Entropy was shown to be a thermodynamic property of the system, which serves as a measure of the unavailability or the degradation of energy. An increase in the unavailability of the total energy of a system is quantitatively expressed by a corresponding increase in its entropy. It is defined by ‘The Camot principle and the concept of the thermodynamic temperature were explained in Section 4.4, The Carnot engine was shown to have the maximum efficiency among all engines ‘operating between any wo given temperature limits. This efficiency is a function of only the reservoir temperatures and is independent of the working fluid. This led to the relationshipa You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.Second Law of Thermodynamics 113 4.13 Oil of specitic heat 3.2 kivkg K is cooled from 495 K to 315 K at a rate of 3000 kg/h by exchanging heat with a large thermal reservoir at a constant temperature of 300 K. ‘What is the lost work in the process? 4.14 Tt has been suggested that a building could be heated by a refrigeration engine operating in a Carnot eycle. The engine takes heat from the outside at 280 K and delivers heat 10 the building at 295 K. How much work would have to he done for every kilo joule heat delivered 10 the building? 4.15 An inventor claims to have developed an engine that produces 1200 kI of work while receiving 1000 kI of heat from a single heat reservoir. Such an engine would violate both the first and second laws of thermodynamics. Do you agree? Why? 4.16 Calculate the molal entropy of fusion and vaporisation of ethyl alcohol which melts at 158.8 K and boils at 351.5 K. The latent heat of fusion and vaporisation are 108 Ki/kg and 855 kJ/kg respectively 4.17 Air at an initial condition of 1.4 bar, 295 K, and 0.3 m’ is compressed to a pressure of 4.8 bar whereby its volume is reduced 10 0.12 m’, Calculate the change in the molal entropy of the gas in this process. Tuke the specific heat at constant volume of air to be 20.52 ki/kmol K. 4.18. A block of copper at a temperature of 825 K and weighing 5 kg is dropped into 50 kg water at 300 K. If there are no heat losses what is the change in entropy of (a) copper, (b) water, and (c) copper and water both considered together? Cp of copper is 0.4 kivkg K fand that of water is 4.2 kI/kg. K. 4.19 A refrigerator is to be used to maintain the temperature of certain storage space at 250 K. ‘The compressor is rated at 250 W and the cooling duty is estimated co be 5 x 10* kI per day. Determine the fra he compressor suns if the refrigerator is used in jon of the time (@) a cold country where the ambient temperature is 290 K and () a tropical country where the ambient temperature 310 K 4.20. How much work must be done in order to cool the air in an otherwise empty room of dimensions 5.0 m x 5.0 m x 3.0 m from 303 K to 295 K when the ambient temperature is (a) 293 K (b) 303 K? Take specific heat of air to be 29 kivkmol K and density to be 1.2 kgim’. 4.21. Liquid helium is produced from its saturated vapour at 4.2 K. The latent heat of vaporisation Of helium at this temperature is 83.3 kJfAkmol. Caleulate the minimum work reguined to produce liquid helium if the ambient temperature is 305 K. 4.22 heat engine absorbs 260 KI of heat from a source at 325 K and yields a work output of 72 KJ rejecting 100 KJ of heat to a reservoir at 300 K and 88 I of heat to another reservoir at 275 K, Does this engine violate the laws of thermodynamics? 423 The heat capacity of chloroform in the range 240 K to 330 K is given by Cp 9147 + 7.5 x 107 T where Cpis in Simo! K and T in K. Calculate the change in molar entropy of chloroform when itis heated from 273 K t© 300 K.114 424 425 426 427 428 429 430 431 432 A -xibook of Chemical Engineering Thermodynamics One kilogram of saturated liquid water at 100 kPa is mixed with 5 kg of superheated steam at 100 kPa and 573 K in an insulated container. Assuming that the pressure remains constant during mixing, calculate the entropy generation due to the mixing process. Ina boat exchanger, ar is heated from 293 K 10 353 K by means of a second air stream which enters the exchanger at 423 K. The molar flow rates of both the streams are equal and the specific heat of air is 29.3 kI/Kmol K. (@) Calculate the entropy change of both the streams and the total entropy change (@) Repeat the above calculations if the cooler air temperature is raised to 393 K. Why could this be achieved only in a counter-current system? A cylinder of free volume 0.283 m* is divided into two compartments by @ piston Inivally the piston is at one end and the eylinder contains 1 kg steam at 423 K. Ae from a supply main at 1400 kPa and 288 K is then admitted slowly via a throttle valve 10 the other side of the piston. Estimate the temperature of the ait when pressure equilibrium is attained. Negleet any heat loss from the eylinde the piston. State clearly the assumptions made. Cy nd assume no heat transfer across 21 Hmol K for air One kilo mole of water is heated at the constant pressure of 1400 kPa from a temper of 294 K to the boiling point and then completely vaporised at this pressu What portion of the heat transferred is unavailable for transformation to work in a heat tengine assuming that the temperature of the heat sink is 283 K? Boiling point of water at 1400 kPa = 468 K. Latent heat of vaporisation = 1960 ki/kg, ‘What is the inerease in unavailable energy for the conditions in Exereise 4.27, if the heat is transferred from a furnace at 1480 K? Determine the entropy of the mixture of two ideal gases A and B in the proportion 1:2. If this mixture is expanded through a throttle from pressure S00 kPa 10 100 kPa what is the entropy change of the universe? i with a heat capacity of 3.2 ki/kg K is w be cooled from 495 K 10 315 K at a rate of 5000 kg/h, An unlimited supply of cooling water at a constant temperature of 303 K is available. Determine the lost work in the process and the thermodynamic efficiency of the process. A hot hydrocarbon oil (Cp = 2.512 ki/kg K) is cooled from 422 K to 339 K in a heat exchanger at the rate of 2500 kg/h. Cooling water at the rate of $000 kg/h enters the exchanger at 294 K, Assume that there is no heat loss in the exchanger. (a) What is the change in entropy of the oil? (b) What is the total change in entropy? (€) How much work could be obtained if the cooling of the oil were cartied out by a reversible Carnot engine rejecting heat to a sink at 294 K? (a) Nitrogen gas (Cp = 30 kI/kmol K) at 1 bar and 300 K is to be compressed to 10 bar and 450 K at a rate of $000 kg/h. Cooling water (Cp = 4.1868 ki/kg K) enters the compressor at 300 K at the rate of 7500 kg/h and leaves at 320 K. Determine the power required by the compressor. (b) For the same conditions of nitrogen as in the previous part, determine the minimum power required by the compressor. The rate of eireulation and the inlet temperature of cooling water remain the same as above,SOME APPLICATIONS OF THE LAWS OF THERMODYNAMICS Engineers would be able to devise methods for improving the efficiency of a process by proper application of laws of thermodynamics. This chapter deals with the thermodynamic analysis of some typical industrial processes using the first and the second laws of thermodynamics. The first section deals with the general energy balance equations and their application 0 some important fluid flow problems. Refrigeration and liquefaction processes are discussed next, with emphasis fon the thermodynamic cycles rather than on the equipment used. In the last sections, the thermodynamic analysis of various power cycles that are commonly used in steam-power plants, internal combustion engines and gas turbines are discussed. 5.1 FLOW PROCESSES Thermodynamics can be used to Find solutions to many fluid flow problems. Some of the basic equations in fluid mechanics are developed using the first and second laws of thermodynamics. However, questions that are related to the mechanism of flow, such as the loss of heat due to friction are not within the scope of thermodynamics. In order to facilitate the application of thermodynamic principles to flow process, we assume that the flow is unidirectional and the fluid properties do not change in the direction perpendicular to the direction of flow. By the latter ideatisation, we mean that the properties at any point in the flow system are average values applicable for the entire cross-section, 5.11 Continuity Equation apa =o oo where p is the ay density, A is the fluid cross-sectional area and u is the average fluid velocity, Equation (5.1) is known as the continuity equation, For steady-state flow process, there is no accumulation of mass within the control volume, and the equation reduces 10 5-xibook of Chemical Engineering Thermodynamics @ Fig. 8.1 Energy balance for a control volume. (pul 62) Denoting the conditions at the entrance to the control volume by subseript 1 and the ‘conditions at the exit by subseript 2, Eg. (5.2) may be re-written as Pima = Pau 5.1.2, Energy Equation The law of conservation of energy for a control volume is given by Rate of accumulation of energy , Net rate of energy out Ww within the control volume by the flowing streams” 2 where @ and Wate the rate at which heat is supplied to the fluid and the rate at which shaft work is done by the fluid respectively Rate of accumulation of energy is dU'ldt, where U' is the total intemal energy within the control volume. The total energy of the fluid stream is the sum of its kinetic energy (KE), potential ‘energy (PE), and internal energy (IE). The law of conservation of energy can now be expressed as NRE) + A(PE) + ATE) ow (3) where Jn is the mass flow rate and Z is the height above a reference plane, The work rate W is made up of two parts—the shaft work W, and the flow-work, the latter being the product of the pressure and the volume of the fluid. The flow work is equal to ApiqPV)] and it is the net work done by the fluid in pushing it into and out of the control volume. We Wy + ADIPYD) 65)Some Applications of the Laws of Thermodynamics 17 Substituting Eqs. (5.4) and (5.5) in Eg. (5.3) and noting that H'= U + PV, the energy equation becomes For steady-state flow process, there is no accumulation of energy within the control volume, and Eq, (5.6) reduces to au’ ar vale ozo = Wy 66) seen 6-% 6 For low systems where he knsic and potential energy changes ae negligible, Eg, 5.) canbe further simp to ant = 0-W, 68) I the fluid enters and leaves the control volume in a single stream, the mass rate of flow remains the same at the entrance and exit. Then Eq, (5.7) becomes Eeea)o-n so ‘This equation is known as the sora! energy balance. For the case, where changes in kinetic and. potential energies are negligible, Bq. (5.9) becomes AH =Q-Ws 5.10) In both Egs. (5.9) and (5.10), Q = (Oth) and W, = si) ‘The ‘total energy balance’ considers only the input and output from the system. For fluid ‘mechanics caleulations, itis customary to express this equation in the form of mechanical energy balance. The mechanical energy balance takes irreversible effects, such as, fluid friction also into account. Equation (5.9) may be put in the following form: ot gars ate my eu From the definition of enthalpy of a fluid [see Eq. (2.9)}, we get dH = dU + Pav + VaP 5.12) Using the first law of thermodynamies (see Eq. (2.5)], = dQ-aw 6.13) For a reversible process, the work done by the fluid is aW= PavA -xibook of Chemical Engineering Thermody Substituting this into Eq. (5.13) and combining the resulting equation with Eg. ( dH =do+VaP 5.14) 12), we get Inegate 5.14) etean the entance a ext ofthe ona volume Then ao f var os) Using this relation, Eq, (5.11) ean be modified to the following form: = Z i p 1 We ME aa ff va 16) If the changes in kinetic and potential energies are negligible, the shaft work is given by * [i van wn ‘The above equations are developed assuming reversible processes. On including the work lost due to the irreversiblities, Eq. (5.16) takes the following form: aw Me gare fl varem ere on 2 Here, F represents the lost work due to friction or mechanical energy dissipated to heat due to irreversibilities in the system. Equation (5.18) is known as the mechanical energy balance. Bernoulli's equation. Bernoulli's equation is a special form of the mechanical energy balance applicable only to non-viscous incompressible fluids, which do not exchange shaft work with the surroundings. For non-viscous fluids, F = 0. The integral in Eg. (5.18) can be evaluated if the functional relationship between pressure and volume is known. For incompressible fluids, volume is independent of pressure, and hence a an ff van=van= 22 1) i > where p is the density of the fluid. Since no shaft work is exchanged, Ws = 0. Using these simplifications, Eg. (5.18) can be written as My eaz+ AP ag 620) 2 D P +42 + 5 = constant 6.21) Equation (5.21) is known as Bernoulli's equation.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.Some Applications of the Laws of Thermodynamics ca Compare Eq. (5.26) with Eg. (5.27). rasan Ba vara glt a0 Equation (5.28) may be written in the following form: pT dS = dp aP 6.29) For flow of gas through a pipe of uniform cross-section, since the flow is in the direction of decrease in pressure (dP < 0), the specific volume increases or density decreases (dp < 0) in the flow direction, The first term on the right is negative and the second term is positive, At a particular pressure, these two contributions to the entropy change will be equal in magnitude so that dS = 0. The maximum velocity is attained by the gas at this condition and it can be evaluated 0 for constant S dp ~aP “ -(§) mm | 5p | 5.30) “The speed of sound in a fluid is evaluated as the square root of the derivative on the right-hand side of Eq. (5.30). Therefore, iy =c%, where c is the sonic velocity. Thus, we see thatthe ‘maximum fluid velocity attained in'a pipe of uniform eross-setion is equal to the speed of sound in the fluid, 5.1.4. Flow through Nozzles A nozzle is a device for converting thermal or mechanical energy into kinetic energy. This is achieved by changing the cross-sectional area available for flow. Nozzles find application in turbines, ejectors, diffusers, ete. In the analysis of flow through nozzles presented below, it is assumed that the flow is isentropic, Relation between A and u. Let us first sce the relationship between cross-sectional area and velocity of the fluid through a pipe of varying cross-section. Equation (5.2), the equation of continuity, expressed in differential form is given below: dupa) =0 This equation may be put into the following form: (Py ut ate) en ig t= apa) 6a The mechanical energy balance (Eq. (5.18}] may be put in differential form as given below: udu +g dZ+VdP + dWs+dF =0122 A -xibook of Chemical Engineering Thermodynamics For frictionless flow (dF = 0) with no work exchange (dW energy (dZ = 0), the above equation gives ), and neglecting change in potential udu+ VaP=0 Noting that V = 1/p, the above equation may be written as aP =~ pu du (5.32) ‘Combining Egs. (5.31) and (5.32) we get the following results: w-E apo-E pus cap a ofa) Because of our assumption of isentropic flow. (d/tdp) in the above equation may be replaced by (APIap)« which was shown to be equal to c*, where cis the sonic velocity. Also, dp can be replaced by dPle*. The resulting equation can be rearranged as a, pe ‘The ratio of actual velocity to the speed of sound is known as the Mach number and is denoted by M. Equation (5.34) may now be written as 5.34) 3? ot (5.35) Using Eq. (5.32), dP may be eliminated from the above equation, Hany -) (5.36) For subsonic velocity of the gas M< 1 and (dA/du) < 0. For supersonic velocity, M> | and (AAldu) > 0. For sonie velocity, M = 1 and (dA/du) = 0. Equation (5.36), therefore, means that if the gas is to be accelerated continuously from subsonic to supersonic velocity, the area of eross- section for flow should first decrease (4A < 0), then remain constant (dA = 0), and finally increase (AA > 0). This principle is used for increasing the velocity of gases beyond Mach number unity in the converging-diverging nozzles (Fig. 5.2). Velocity at the throat. It is clear that the maximum velocity attained by the gas in the ‘converging section of the converging-diverging nozzle is the sonic velocity. Therefore, referring to Eq, (5.30), we see that the velocity at the throat is given by ar = (5.37)Some Applications of the Laws of Thermodynamics 123 | 1 j+—— Divergent section ——4 1 1 1 T- ‘onvergent c. Reservoir Receiver Fig. 5.2. The convergent-divergent nozzle. Critical pressure ratio. The relationship between pressure and velocity in a nozzle is given by Eq. (5.32), which may be put in the following form: #_vap (538) e At the inlet to the nozzle, let uw = and P= Po, and at any plane normal to the flow within the nozzle, let the velocity and pressure be u and P respectively. Assuming isentropic flow of ideal jgases, the pressure and volume are related as PV’ = constant, Substituting this in Eg, (5.38) and integrating, we get se ("| - Pip" = constant for isentropic expansion of ideal gases, Suppose that the nozzle is connected between a reservoir at pressure Py and a receiver at pressure P,, Flow through the nozzle occurs when P, is less than P) and the velocity of the fluid at the throat is maximum. On further reduetion of the receiver pressure, the flow rate and the velocity through the nozzle increases, A limiting value is attained when the velocity at the throat becomes sonic. The pressure at the throat at this condition is Pc, the critical pressure, The criticala You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.a You have either reached 2 page thts unevalale fer vowing or reached your ievina tit for his book.Some Applications of the Laws of Thermodynamics 129 OP beet OFT) oe ‘The work required for compressing an ideal gas may be written in terms of the initial and final temperatures as well, For an ideal gas, AH = Cpi\T. Equation (5.44) gives Ws=-AH = CH - Ts) 6.7) ‘The work computed by Eq. (5.46) or by Bg. (5.47) provides the value for the numerator in Ea. (5.45), Isothermal compression. For reversible isothermal compression of a ges, Eq. (5.10) becomes Ws=Q-aH Since Q = TAS under this condition, we have Ws = TAS - aH (6.48) IT the gas is ideal AH = 0, because, the enthalpy of ideal gas depends only on temperature, Also, p as=Rin 2 2 For ideal gases, Eg, (5.48) therefore simplifies to Wo= Rtn =r in ?, v (5.49) Equation (5.49) gives the shaft work required in isothermal compression of ideal gases. The same result is obtained from Eq. (5.17) also by replacing V by RTP. Multi-stage compression. The reversible isothermal and adiahatie paths for the compression ‘of an ideal gas from an initial pressure P, to a final pressure P is shown in Fig. 5.4. Dc P; 4 Reversible adiabatic 2 Reversible isothermal rife A Volume Fig. 5.4 Adiabatic and isothermal compression on a P-V diagram,130 A -xibook of Chemical Engineering Thermodynamics The area bounded by the curves, the pressure axis, and the horizontal lines drawn at P and P = P: gives the integral [V dP evaluated between limits Py and Ps, which, by Eq, (5.17), is the shaft work required. From Fig. 5.4, itis evident that compression along the isothermal path requires less work compared to the adiabatic path. The actual compression takes place along a path intermediate to these two limiting paths. However, the isothermal path can be approached in practice by compressing the gas in stages with inter-stage cooling at constant pressure, In Fig. 5.5, itis shown that the compression of gas from pressure P, to pressure P; achieved in three adiabatic steps. P, Adiabatic compression Pp Three-stage adiabatic compression with intercooling Isothermal compression Pressure ’, Volume Fig. 5.5 P-V diagram of a three-stage adiabatic compression with interstage cooling. ‘After the first and second stages the gas is cooled to the original temperature at constant pressure. “The actual path traced by the gas is shown with arrows and it is very close to the isothermal path for compressing the gas between the same pressure limits. The shaded area in Fig. 5.5 is the saving in the work requited for compressing the gas from pressure P, to pressure P, by using a three stage compressor with inter-stage cooling over the work required in a single-stage compressor employing the same compression ratio, Because of mechanical difficulties, a compression ratio greater than 5 cannot be attained in single-stage reciprocating compressor, Multi-stage compressors are used to develop high compression ratios, The main advantage of this compression is that it allows inter-stage cooling and thereby aan isothermal operation is closely approached. This results in reduction in the work done for compression, ‘The work requirement in a multi-stage compressor is the sum of the work requirements for the individual stages. For a two-stage compressor in which an ideal gas is compressed from pressure Pj to P* in the first stage and cooled to the initial temperature T; before it is sent t0 the second stage for the final compression to a pressure P., the total work required according to vee staf (E (8 aan