Tee rs Engineerin eis: .Tata McGraw-Hill Published by Tata McGraw-Hill Publishing Company Limited, 7 West Patel Nagar, New Delhi 110 008 Copyright © 2008, by Tata McGraw-Hill Publishing Company Limited. No part of this publication may be reproduced or distributed in any form or by any means, electronic, me- chanical, photocopying, recording, or otherwise or stored in a database or retrieval system without the prior written permission of the publishers, The program listings (if any) may be entered, stored and executed in a computer system, but they may not be reproduced for publication. This edition can be exported from India only by the publishers, Tata McGraw-Hill Publishing Company Limited ISBN-13 : 978-0-07-066932-1 ISBN-10 : 0-07-066932-5 Managing Director: Ajay Shukla General Manager: Publishing—SEM & Tech Ed: Vibha Mahajan Sponsoring Editor: Shalini Jha Editorial Executive: Sandhya Chandrasekhar Senior Copy Editor: Dipika Dey Junior Manager—Production: Anjali Razdan General Manager: Marketing—Higher Education & School: Michael J Cruz Product Manager: SEM & Tech Ed.: Biju Ganesan Controller—Production: Rajender P Ghansela Asst. General Manager—Production: B L Dogra Information contained in this work has been obtained by Tata McGraw-Hill, from sources believed to be reliable. However, neither Tata McGraw-Hill nor its authors guarantee the accuracy or completeness of any information published herein, and neither Tata McGraw-Hill nor its authors shall be reponsible for any errors, omissions, or damages arising out of use of this information. This work is published with the under- standing that Tata McGraw-Hill and its authors are supplying information but are not attempting to render engineering or other professional services. If such services are required, the assistance of an appropriate professional should be sought. Typeset at Bluckans Information System Pvt. Ltd., B-92, Sector-64, Noida, and printed at Adarsh Printers, C-S0-S1, Mohan Park, Naveen Shahdara, Dethi-110032, Cover Printer: Rashtriya Printers RYLCRRAXRQLOXContents: Preface xiii Acknowledgements xv 1. Thermodynamics i 1,1__Introduction _ 1.2__ Terminology _/ 1,3 _ First Law of Thermodynamics __$ 1.4 The Second Law of Thermodynamics __/3 1,5___ Equilibrium and Spontaneity 15 1.6 Third Law of Thermodynamics 18 :7__ Thermodynamic Applications to Physical Equilibria 1.8 Thermodynamic Applications to Chemical Equilibria 20 L9___ Maxwell Relations _24 Solved Examples 26 Review Questions __28 2. Phase Rule 29 2.1 Phase Equilibrium 29 2.2__Definitions _29 2.3__Gibbs’ Phase Rule 30 24 Application of Phase Rule to One-Component Systems _30 2.5 Phase Rule for Two Component Systems 33 2.6 Application of Phase Rule for Two Component Metal (Alloy) Systems 34 2.7___Substitutional Solid Solutions __35 2.8 Eutectic Forming Systems __37. 2.9 Systems Involving Compound Formation 39 2.10 Partially Miscible Solids 40 2.11 Interstitial Solid Solutions: Iron-Carbon System 42 Solved sles. 46 Revi sstions 46 3._Solid State 48 3.1__Introduction__48 3.2__ Amorphous and Crystalline Solids7 plications of eit Meennonicals 4a is Elst ysis and Polarisation 116 4.19 Overvoltage 1/8 4.2 Electrolysis 87 43 Faraday’s Laws of Electrolysis 88 44 Transference of Transport Number 89 45 Electrolytic Conductance 90 4.6 Ionic Mobility 94 of Half-Cells or Sins 41 Thermodynamics of lecode Ptenals i 4D 413 Tencenes cfg nears tei 107, 5 Caleulation of Cel. emf Values fom Single Electrode Potentials H2 10 Copyrighted materialContents vii 4.20 Electrochemical and Electrometallurgical Applications 119 4.21 Commercial Energy Producing and Storage Cells__129 4.22 FuelCells 136 Solved Examples __141 Questions 143 5. Adsorption 145 S.1__Introduction _J45 5.2___Adsorption by Solids __145 5.3 Adsorption of Gases by Solids 145 5.4 Adsorption of Solutes by Solids 157 5.5 Adsorption Techniques _/52 5.6 Applications of Adsorption 153 Solved Examples 154 Review Questions 154 6, Kinetics of Chemical Reactions SSCS ‘i Saceate be 6.3 Order and Molecularity 157 64 Rate Expressions of Different Orders 1/58 6.6 Effect of Temperature on Reaction Rates /62 6.2__Theories of Reaction Rates _J64 6.8 of Reactions 166 69 Catalysis 170 6.10 Enzyme Catalysis 186 6.11 Photochemical Reactions 189 Solved Examples __200 Review Questions 201 7. Organic Reactions 203 7.1 Introduction 203 7.2. Types of Organic Reactions 203 7.3 Reagents in Organic Reactions 203 14__Reaction Mechanisms 204 7.5 Addition Reactions 207 7.6 Mechanism of Addition Reactions 207 7.7 Substitution Reactions 209 7.8 Elimination Reactions 212Contents 7.10 Rearrangement Reactions 216 Review Questions 217 8. Polymers 8.1 Introduction 219 8.2 Nomenclature and Terms Used in Polymer Science 219 8.3 Types of Polymerisation 22/ 8.4 Mechanism of Addition Polymerisation + 222 8.5 Methods of Polymerisation 225 8.6 Molecular Weight and Molecular Weight Distribution 227 8.7 Structure and Properties of Polymers 228 88 Plastics 232 8.9 Fabricating Methods 234 8.10 Important Thermoplastic Resins 237 8.11 Important Thermosetting Resins 244 812 Elastomers __248 8.13. Polymers Related to Natural Rubber 253, 8.14 Synthetic Rubbers 253 8.15 Fibers 255 8.16 Silicones 257 8.17 Specialty Polymers 258 Review Questions __270 9. Chemical Methods of Analysis 272 44 5 ss 9.2 Volumetry 272 5 euaiids a8 9.4 Precipitation Titrations 275 9.5 Complexation Titrations 277 is Redes tliat oa 9.7 Gravimetry 282 Solved Examples 286 Revi tions 287 10. Instrumental Methods of Analysis 288 10.1 Introduction _288 10.2 _ Spectroscopic Methods __288 10.3 Atomic Spectroscopy __29/ 10.4 Molecular Spectroscopy 296 10.5 Magnetic Resonance Spectroscopy 310Contents ix 10.6 Electroanalytical Methods 3/6 10.7 Chromatographic Methods 325, 10.8 Thermal Methods of Analysis 336 Review Questions 341 11. Energy Sources 343 1.1 Introduction 343 1L2__Fossil Fuels __344 sta B 11.4 _ Relative Merits and Demerits of Solid, Liquid and Gaseous Fuels 344 wietat 5 A 1.6 Calorific Value _345 11.7 Coal: Formation and Ranking 349 11.8 Beneficiation, Cleaning and Storage of Coal___350 11.9 Analysis of Coal 350 11.10 Pulverized Coal 354 11.11 Secondary Fuels ftom Coal 354 11,12 Manufacture of Metallurgical Coke _355 11.13 Petroleum: Composition and Classification _358 11.14 Secondary Liquid Fuels from Petroleum 367 11.15 Synthetic Petrol 365 11.16 Purification of Gasoline, Diesel Oil, Kerosene and Lubricating Oils 365 11.17. Liquid Fuels from Coal 366 11.18 Coal Tar 367 11.19 Characteristics of Fuels for Internal Combustion Engines 368 11.20 Gaseous Fuels 373 11.21 Gaseous Fuels from Coal 374 11,22 Gasification of Oils 377 Determination of Efficiency of Combustion 379 Nuclear Energy 387 Solar Energy 388 Hydro Power 393 Wind Energy 394 Biofuels and Biomass 394 Geothermal Energy 394 Ocean Thermal Energy 395 Tidal and Wave Power 395 Hydrogen Energy 396 Solved Examples 396 Review Questions 400aOR * we 12. Chemistry of Engineering Materials 402 12.1__Intraduction _402 12.2 Cementing or Binding Materials 402 123 Lime 402 12.4 Gypsum Plasters 404 12.5 Cement _404 12.6 Ceramics __400 12.7_Clay Products 4/1 128 Glass 4/2 129 Refractories 414 12.10 Abrasives 420 12.11 Composites 421 12.12 Lubricants 433 12.13. Adhesives 445 12.14 Explosives 447 12.15 Rocket Propellants 449 12.16 Nanomaterials __45/ Review Questions 465 13. Corrosion and its Control) CT a4 ‘ 2 13.2__Types of Corrosion 467 13.3_Dry Corrosion 467 13.4__Wet Corrosion _469 13.5 Atmospheric Corrosion __ 473 56 Selamat 7 13.7__ Stress Corrosion and Stress Cracking __473 13.8 Microbiological Corrosion 474 13.9 Intergranular Corrosion 474 SiN Emin Gackt 13.11_Stray-Current Corrosion __474 13.12 Factors Influencing Corrosion 475 13.13 Testing and Measurement of Corrosion 477 13.14 Protective Measures against Corrosion 477 13.15 Protective Coatings 482 13.16 Metallic Coatings 483 13.17_Non-Metallic Inorganic Coatings 485 13.18 ic Coatin, 487 13.19 Types of Paints and their Uses 490Contents - xi 9.00. “Detecis tn’ Patnt FH 2 13.21 _Vamishes _493 13.22 Enamels and ers 493 Review Questions 494 14, Water Treatment 2. CC“C‘“‘i S'S: 14.1 Introduction _495 14.2 _ Quality of Water for Different Uses 495 143 Analysis of Water 495 144 Domestic Water Supply 500 14.5 ___ Water Treatment (Softening) SOS Bal Roller T 5 14.7 __ Boiler Feed Water Treatment _513 14.8 Cooling Waters = 5/5 Disaatinalinase Solved Examples 518 Review Questions 520 15. Pollution of the Environment and its Control .-_———s521 15.1 _ Environment and Its Pollution _52/ 15.2 Environmental Segments 527 15.3 Atmosphere 52/ : poe es 1$.5 AirPollution Monitoring 529 15.6 Air Pollution Control 530 15.7 Indoor Air Pollution 532 15.8 Water Pollution 533 15.9 Sewage Treatment and Disposal 534 15.10 Wastewater from Industries _538 15.11 Modern Wastewater Treatment Techniques 54] 15.12 Soil Pollution 542 15.13 Municipal Solid Waste Management 542 15.14 Hazardous Wastes 548 15.15 Radioactive Wastes 550 15.16 Green Chemistry and Environmentally Clean Technology 551 Solved Examples 554 Review Questions 554 Index 557Copyrighted materialPreface Engineering and technology have become inter-disciplinary with chemical, physical and biological sciences contributing immensely to the development of engineering practices. Applied chemistry is a fascinating area with profound implications for engineers as well as biologists. Materials fabricated and used in our daily life are obviously derived trom chemicals, both natural and synthetic and their range of utility are growing day by day. It is imperative that engineers of different disciplines aequire sufficient knowledge of the materials and their characteristics for making proper selection of their end use applications. The use of tailor made materials of specific end uses have almost become the order of day. Fine tuning the properties of materials through the development of necessary chemical processes are in the realm of practicing chemists but it is the job of practicing engineers to define the basic requirements of specific end uses and to evaluate the finished products for stated purposes. Hence, a basic understanding of the chemistry of materials and processes is a must for an engineer or a technologist. A proper perspective of applied chemistry requires a sound knowledge of the underlying principles. The present book envisages at providing the necessary introduction of the chemical principles involved and applications of various materials and devices in a comprehensive manner yet understandable to the students: aspiring to become practicing engineers. Objective ‘The book has been prepared to cater to the needs of engineering students with sufficient background of chemistry acquired at the Senior Secondary level. The objective is to present the necessary theoretical aspects required for understanding intricacies of the subject and also give sufficient exposure to the applied chemistry aspects in different disciplines of engineering. Universities in India have prescribed syllabi with varying emphasis on diverse topics of interest to engineers. The depth of coverage of each topic varies, with some syllabi oriented towards applied aspects, while others stressing more on characterisation, particularly with instruments. The present book has been prepared taking into account the requirements of engineering students of different Universities, giving an in-depth coverage of a wide range of topics and hence will be useful for engineering & technology students and also to teachers in preparing for their lectures.xiv Preface Organisation The presentation as well as treatment of topics are user friendly and would make the reader comfortable while going through the book. The first few chapters deal more with the fundamental aspects such as thermodynamics, chemical kinetics, solid state, electrochemistry and phase equilibria as well as applications of relevance. Two chapters have been presented exclusively on analytical chemistry involving the classical and instrumental methods to make engineers feel at ease and also give them an insight with regard to the use of different methods by chemists for characterising materials. The last few chapters deal with application oriented topics of relevance to engineers and technologists. Features This book on Engineering Chemistry is written with the intention of discussing the required topics atthe right level keeping in mind the practical applications of the subject inthe field of engineering. It offers an exhaustive coverage of the topics (especially the applications) and lucid explanation of concepts as per the present day needs and practices. * The book follows an application based approach. There is a perfect link between theoretical aspects and relevant applications. © Theory and fundamental aspects are discussed in the first 6 chapters followed by application oriented topics with appropriate theory in the later chapters. Coherent organisation of the main topics followed by a logical progression of subtopics make the subject easy to understand. * A methodical approach has been followed while dealing with the conceptual and theoretical aspects of all topics. For more clarity, tables and figures are interspersed throughout the book. ‘To enhance comprehension, solved examples have been included in many chapters. Review questions enable recall of concepts explained in each chapter. Important topics such as Photochemistry in Natural Systems and Industries (Chapter 6), Pollutions of Environment (Chapter 15), Engineering Materials (Chapter 12) and Instrumental Methods of Analysis (Chapter 10) have been dealt with appropriately. Hence, this book proves to be a very good reference for updating knowledge and creating awareness of recent techniques and processes. Dedicated Web Support Readers are encouraged to login at our website hitp://www.mhhe.convsivasankar/ec which contains a wealth of digital content, Instructors can access Solutions Manual and PowerPoint slides, which can be used as teaching aids. Students can refer web links for in-depth research, and additional problems for practice. The website also features model question papers with solutions—an effective guide for exam preparations.I would like to acknowledge the editorial and sales staff of McGraw-Hill Education, particularly Vibha Mahajan and Sriram Kumar for initiating me into this project and Sandhya Chandrasekar for her persistent efforts enabling me to complete this project. My special thanks are due to my friends and well-wishers, particularly Professors Dr V Sadasivam, Dr K Rengaraj (retd,) and Dr GR Rajarajeswari of Chemistry Dept., Anna University, Chennai for their constant encouragement and help in preparing the manuscript. I extend my gratitude to my colleagues and the authorities of Anna University for the academic ambience. My thanks are also due to my wife and children who have been supportive throughout. 1am indebted to the following reviewers for providing us with excellent suggestions. AS Singha National Institute of Technology, Hamirpur, Himachal Pradesh Dr PK Tripathy North Eastern Regional Institute of Science and Technology, Nirjuli. Arunachal Pradesh Dr Apama Singh People’s College of Research & Technology, Bhopal, Madhya Pradesh Dr Indu Bala Sharma Gurgoan Institute of Technology and Management, Gurgaon, Haryana Mr Krishan Kant Upadhyay Galgotia College of Engineering & Technology, Greater Noida, Uttar Pradesh Dr Poonam C. Kumar Raj Kumar Goel Institute of Technology, Ghaziabad, Uttar Pradesh Dr PPGiri Galgotia College of Engineering & Technology, Greater Noida, Uttar Pradesh Dr Preeti Jain Medicaps Institute of Technology and Management, Indore, Madhya Pradesh Dr Sandeep Tomar Meerut Institute of Engineering & Technology, Meerut, Uttar Pradesh Dr Satish Mahilla Engincering College, Bikaner, Rajasthan Dr Yasmin Akktar Alfath school of Engineering and Technology, Faridabad, Haryana Dr SK Aggarwal Amritsar College of Engineering and Technology, Amritsar, Punjab Dr Harshita Sachdeva Mody Institute of Technology and Science, Lakshmangarh, Rajasthanxvi Ashish M Desai Sarvajanik College of Engineering, Surat, Gujarat VS Khadilkar VET’s Vivekanand College of Engineering, Mumbai, Maharashtra Dr Deepa Kapoor CK Pithawalla College of Engineering & Technology, Surat, Gujarat Prof. Anjali Kirkire Thadomal Shahani College of Engineering, Mumbai, Maharashtra Mr Abhranil De Hooghly Engineering & Technology College, Hooghly, West Bengal Dr Jnan Prakash Naskar Jadavpur University, Kolkata, ‘West Bengal Mr Indranil Ghosh Netaji Subhash Engineering College, Kolkata, West Bengal I Mohamed Ismail Crescent Engineering College, Chennai, Tamil Nadu S Vasantha Kumar Karunya University, Coimbatore, Tamil Nadu S Shanmugam Rajalakshmi Engineering College, Chennai, Tamil Nadu TK Arumugam Sri Venkateswara College of Engineering, Chennai, Tamil Nadu N Rajendran Madras Institute of technology, Chennai, Tamil Nadu G Selvakumari Coimbatore Institute of Technology. Coimbatore, Tamil Nadu Somasekhara Reddy G Pulla Reddy Engineering College, Kurnool, Andhra Pradesh A. Ramachandra Rao Sir C R Reddy Engineering College, Eluru, Andhra Pradesh Dr G V Subba Reddy, INTU College of Engineering, Pulivendula, Andhra Pradesh Dr MC Somasekhar Reddy G Pulla Reddy Engineering College, Kurnool, Andhra Pradesh BB Patra. College of Engineering and Technology, Khandagiri, Orissa Dr Biswajit Mishra Krupajal Engineering College, Bhubaneswar, Orissa ‘Suggestions towards improving the text for removing any mistakes and shortcomings are most welcome and would be gratefully acknowledged. B SivasankarTHERMODYNAMICS 1.1 Introduction Thermodynamics means heat power and this branch of physical science deals with the interconversion of energy that accompanies all changes that occur in nature. For example, motion of # particle, combustion of coal, growth of tissue in a living species etc., are diverse processes that are accompanied by interconversion of energy. The most common form of energy is heat which may be formed from chemical energy, mechanical or electrical energy and in tum is converted into any of these forms. Thermodynamics may be studied by any of the two approaches, namely, classical and statistical. Classical thermodynamics also called reversible ot equilibrium thermodynamics deals with macroscopic ‘or bulk properties of matter observable our day-to-day life. Statistical thermodynamics involves the application of classical or quantum mechanics in the evaluation of thermodynamic properties of a large collection of atoms and molecules in 2 microscopic view point. Properties of substances subjected to extremes of temperature and pressure can be predicted by a statistical approach combining the computational techniques with quantum mechanics. Classical thermodynamics provides solutions to most engineering problems by considering changes in macroscopic properties and hence this chapter deals with this approach. Thermodynamics is based mainly on two laws, the first and second faws of thermodynamics. These laws are based on experimental observations on macroscopic systems and are applicable to all phenomena in nature. These laws have been accepted as no contradictory evidence has yet been obtained. ‘The first law of classical thermodynamics deals with direct conversion of heat into other forms of energy. Energy changes that accompany processes are considered, but the law is not concemed with the direction in which such changes in energy occur. The first law is useful in the quantitative study of energy changes in chemical reactions (thermochemistry) and in heat-mechanical work relationship. The second law of thermodynamics specifies the direction of eergy changes and is useful in predicting quantitatively the energy released and the formation of products in chemical reactions under a given set of conditions. Thermodynamics deals with systems in equilibrium and is not concerned with the rate at which equilibrium is attained as time is not considered asa variable and hence does not appear in thermodynamic equations, The rate of chemical processes is the domain of kinetics. 1.2 Terminology Thermodynamics is an abstract science with terms and language which need to be defined and understood. 1.2.1 System, surroundings and boundaries A system in thermodynamics is defined as a part of the matter separated from its surroundings by arbitrarily chosen, imaginary or real boundaries. The system chosen may be investigated either2 Engincering Chemistry theoretically or experimentally. A theoretical system is ideal and amenable for mathematical analysis while an experimental system isa real one. The system is homogenous if it comtains a single phase having physical and chemical properties identical throughout the system. A heterogeneous system will have more than one phase each phase having its own distinct physical and chemical properties. Surroundings include other systems in the immediate vicinity of the chosen system. The surroundings interact with the chosen system by an exchange of matter or energy. One may consider a gas (system) in a balloon (boundary) surrounded by air (surrounding) or a liquid (system) in a beaker (wall of the beaker being the boundary) immersed in a water bath (surrounding) as examples of the terms defined. Any change in the surroundings brings a change in the system but not in the boundary. A boundary may permit flow of heat into or out of the system if it is diarhermic. In contrast an adiabatic boundary (¢.g., Walls of a thermos flask) does not permit heat transfer. Depending on the nature of the boundary three types of systems are identified. (3) Isolated system; one which cannot exchange matter or energy with its surroundings and whose mass and energy remain constant. No work can be done by or on this system. An example of an isolated system is a reaction occurring in a sealed vessel completely insulated from its surroundings. The universe can be considered as an isolated system as it docs not have any surroundings. However, a perfectly isolated system does not exist. (ii) Closed system allows exchange of energy but not matter with its surroundings e.g., a sealed flask containing a gas or a liquid surrounded by a water bath, the walls of the flask permit only heat transfer to the water in the bath whose temperature can thus be altered. Such a closed system permits exchange of heat or work between the system and its surroundings but not the contents (matter). (iii) Open system is capable of exchanging both matter and energy with its surroundings. Examples of open systems include living systems which interact with surroundings exchanging matter and energy or reactions conducted in open vessels. 1.2.2. State of system and process The state of a system is defined by characteristic macroscopic properties such as temperature (T), pressure (P), volume (V), mass (M), composition (C), etc. A system is said to have undergone a change of state when one or more of these properties (variables) change from their initial values. A system undergoes a change from one state to another by a path which is specified by giving the initial state of the system, the sequence of intermediate steps and the final state. The path by which a system undergoes change from an equilibrium state to another over a period of time is called a process, which describes the manner of change. Thus an isothermal process occurs at constant temperature. A system under ‘goes an isothermal process when it is surrounded by a thermostat and maintains a constant temperature by exchanging heat with the surroundings. A system such as a reaction occurring in an open vessel at atmospheric pressure is said to undergo isobaric process (change of state at constant pressure). Isobaric process is always accompanied by a volume change. /sockoric process involves change of state under constant volume. In an adiabatic process heat is not allowed to enter or leave the system. The system is thermally insulated and the temperature of the system may increase or decrease. A process is considered as a cyclic process if a system undergoes change from state 1 to 2 by a certain path and retums to its original state by the same or a different path then the system is said to have gone through a cycle of change. 1.2.3. State functions ‘Thermodynamic properties which depend onty on the present state of the system and are independent of the past history or the path by which the state was reached are called state functions. These include the macroscopic properties already mentioned in the previous paragraph as well as other properties suchThermodynamics 3 as internal energy (F). enthalpy (H). entropy (S), free energy (G). ete. Each state function has a definite value for a given state. Since a state function depends only on the present state of a system, a change in any state function depends only on the initial and final states of the system and not on the path of change. The change in a state function in a cyclic process is equal to zero. ‘Two types of state functions or properties are characteristic of a system. Properties which depend on the amount of the substance present in the system are called exiensive properties. The mass and volume of a system are examples of extensive properties. Properties which are independent of the amount of substance present in the system are called intensive properties or intensive factors. Examples of intensive properties include temperature, viscosity, refractive index, surface tension ete. which hi the same value in any part of the system at equilibrium, Extensive properties are additive whereas intensive properties are not. The value of an intensive property is the same in any part of the system at equilibrium. An extensive property becomes an intensive property once the unit amount is specified. ‘Thus mass and volume are extensive properties. but density (mass/unit volume) and specific volume (volume/unit mass) are intensive properties. Similarly heat capacity is an extensive property whereas specific heat is intensive. In general the ratio of two extensive properties is intensive, Changes in the energy are the multiplication products of an extensive property with an intensive property. Thus the heat energy absorbed by a system is given as the product of the mass and specific heat, 1.2.4 Equilibrium A system is said to be in a state of equilibrium if its properties remain constant and do not change with time. A system is in thermal and mechanical equilibrium if its intensive properties such as pressure and temperature remain the same in any part of the system. If the chemical composition of the system remains unaltered with time the system is said 10 be in chemical equilibrium. A system in thermal, mechanical and chemical equilibrium is said to be in thermodinamic equilibrium and thermodynamics is primarily concerned with a study of systems in equilibrium. A system exists in a non-equilibrium state, for example, the temperature or pressure may be different in different regions of the same system. If the relaxation time, that is, the time required to restore equilibrium conditions is longer compared to an observable time then the system is said to be in a metastable state, a state which appears to be in a state of equilibrium even though it is actually in a non-equilibrium state. For example, the high temperature forms of silica, namely, crystobalite and trydimite (metastable states) exist simultaneously in the earth’s crust as they do not change over to the thermodynamically stable quartz within a reasonable time limit. 1.2.5 Reversible and irreversible processes A process is said to be reversible when a system undergoes a change from one state to another through a number of steps, the system being in equilibrium with its surroundings with respect to temperature and pressure at each step. The energy change with each step, in a reversible process ean be reversed in its direction by small or infinitesimal changes in the thermodynamic variables such as temperature or the pressure acting upon the system. A system which has undergone a reversible process can be restored to its, original or initial state with an infinitesimal change in the external system. Two important requirements for a process to be reversible are (i) the process must be carried out slowly through a number of states of infinitesimal change and (ii) the process must not experience any friction, and there should not be finite temperature differences. Reversible processes are thus theoretical or imaginary. However, itis possible to approach closely the condition of reversibility at least in a few cases. An example of such a proce: occurs in a Daniel cell in which the chemical energy is converted into electrical energy in the4 Engineering Chemistry cell and by applying an emf from an extemal source slightly greater than that generated by the galvanic cell, the direction of energy flow is reversed and the electrical energy can be converted into chemical energy. ‘An Iniarstb prices one ta whiGh the spunea ox ts ooroondlags eaidergy Gian milden changes and are not restored to their initial state. Almost all natural processes are irreversible processes. Examples include the flow of water downhill, flow of heat from a hot body or a region of higher temperature to a cold body or region of lower temperature, flow of gases from a high pressure region to a Jow pressure region etc. Irreversible processes are also called spontaneous processes since the direction of the process is spontaneous. Reversible processes are amenable for mathematical analysis. The state functions associated with the initial and final states of a system undergoing changes irreversibly may be computed by considering a hypothetical reversible path. 1.2.6 Measurement of temperature The science of measurement of temperature called thermometry is based on the zeroth law of thermodynamics, according to which two systems in thermal equilibrium with a third system are in thermal equilibrium with each other. Measurement of temperature depends on the changes in observable physical properties such as a volume change of a liquid (e.g., mercury or ethanol) held in a capillary tube, emf in a thermocouple, or a variation of electrical resistance of metal or its oxide (in a thermistor), etc. The temperature indicated by the temperature measuring device or thermometer is taken as the temperature of the system because the thermometer and the system are in thermal equilibrium with each other. Measurement of temperature depends on the measurement of the physical property at two fixed points and assuming a linear property-temperature relationship between the two fixed points. Thus freezing point of water (ice point) and boiling point of water (steam point) at one atmospheric pressure were fixed as the lower reference point (0 in Celsius and 32 in Fahrenheit scales) and the higher reference point (100 in Celsius and 212 in Fahrenheit scales) respectively. The volume changes of liquids between the two fixed points are assumed to be linear with temperature. In order to have a temperature scale independent of the nature of the thermometric substance; an absolute scafe or Kelvin scale of temperature was proposed using an ideal gas as the thermometric substance. The absolute scale is based on the variation of the pressure of a given mass of ideal gas at constant volume, with temperature as given by the equation, P,=Pll tap aay where P, and P, are the pressures of the gas at 1° C and 0° C respectively and a, is the coefficient of pressure change. The value of the coefficient (fraction by which the pressure ineredses for every degree rise in temperature) was determined to be 36.61 « 10° C-! equal to 1/273.15 for all gases in Celsius scale and 459.7 in Fahrenheit scale. The absolute temperature T can be written as T=WVa,+¢ (1.2) T= 273.15 +1 in Celsius scale or 459.7 + ty in Fahrenheit scale ‘The value of 7 = 273.15 K ift= 0° C and T= 0 K if = -273.15° C. The absolute zero of temperature is the lowest conceivable temperature. 1.2.7. Heat, work and energy When two systems having different temperatures are in contact with each other, heat flows from the system having a higher temperature to the one at a lower temperature. Heat is the energy transferredThermodynamics 5 because of the temperature difference between the systems. The amount of heat transferred g (or energy change) is proportional to the difference in temperature AT or q = CT where C is the heat capacity defined as the quantity of heat required to raise the temperature of a body by one degree. Heat capacity is an extensive property as it depends on the amount of the substance as well as the natnre of the substance. ‘The quantity of heat required to raise the temperature of one gram of the substance by 1° C is called specific heat and the amount of heat required to raise the temperature of one mo! of a substance by 1° C is called molar heat capacity. The quantity of heat is expressed in calories, one calorie is defined as the quantity of heat required (o raise the temperature of 1 g of pure water by 1° C at 15° C (1 cal = 4.184 J) The energy of a system is its capacity to do work and the transter of energy between systems or system and surroundings may occur through work. Work can be done by a system only when it is mechanically linked to its surroundings and when it is moving against some force originating from the surroundings acting on the boundary. The work may be in the form of expansion or compression called the pressure-volume work. The pressure-volume work may be explained by considering a system such as a cylinder having a cross-sectional area A containing an ideal gas and fitted with a weightless and frictionless piston, It is necessary to consider the hypothetical situation of a weightless piston to know accurately the external pressure and a frictionless piston because friction will cause heat and we are ring only the energy transfer in the form of work and not heat. If the gas is allowed to expand the opposing extemal pressure P resulting in the displacement of the piston by a distance dr the infinitesimal work done by the gas is dw = Edr (3) where the force F acting on the piston is given as the product of externa! pressure P and the cross- sectional area of the cylinder A and hence the above equation may be written as dw = P.A.dr a4) Since the product A.dr = dV, the volume swept by the piston while moving by a distance dr, dw = Pav ‘Thus the work done by the gas is equal to a change in volume against the is used to indicate that the quantity considered is not an exact differential while the symbol d is used to indicate that changes in properties are exact differentials. The total amount of work done by the gas is obtained by integration of the volume change that occurred between initial value V; and the final value V,. gl Totalworkdone =f P.dv 6) inti Work done by a system may be in the form of mechanical, electrical or gravitational work. Thus energy is the property of the system and the transfer of energy appears as heat or work and hence these are not properties of the system, Energy has the dimensions of mass = (length)? * (time)? and is expressed in units of ergs, joules or calories while work is expressed in ergs (dyn-cm) or in joules (Newton-meters, N-m or volt-coulombs). 1.3 First Law of Thermodynamics The first law of thermodynamics also known as the principle of conservation of energy was enunciated by Clausius, Kelvin and Helmboltz based on a number of experimental observations. The law may be stated in more than one way as follows:6 Engineering Chemistry Energy can neither be created nor destroyed but it can be transformed from one form into another. Or The total energy of the system and its surroundings musi remain constant. Einstein's relationship E = me? indicates that energy can be created by the destruction of mass, as if contradicting the first law of thermodynamics. But it should be noted that in any energy conversion, conservation of mass and energy together is to be considered. In chemical reactions the conversion of mass into energy is negligible and hence the first law is concerned only with the conservation of energy alone. Every system has a store of energy called the internal energy or total energy E which depends on the pressure, volume, temperature, mass and composition of the system. It includes all forms of energy associated with the system such as potential energy, kinetic energy, vibrational energy, rotational energy te. of the constituent atoms and molecules and the manner in which the atoms are bonded in the molecules. It is a state function and hence the absolute value of the internal energy of a system cannot be measured, but changes in the internal energy can be measured in terms of the heat and work exchanged between the system and its surroundings. The direction of the transfer of energy in the form of heat (q) or work (w¥) between a system and its surroundings is indicated by a sign convention as follows. Heat gained or absorbed by a system is given a positive sign (+q) and heat evolved from the system or lost by the system is given a negative sign (~q). Similarly the work done by the system on the surroundings (e.g., expansion of a gas) is given a positive sign (+w) while work done on the system (e.g., compression of a gas) a negative sign (-w). The first law of thermodynamics can thus be expressed in a mathematical formulation as q=AE+worAE=q-w ay For infinitesimal changes, the above equation may be written as dE = 89 ~ bw (8) ‘The total energy of a system and its surroundings must remain constant in a cyclic process in which the system goes from one state to another and returns to its original state through a series of steps; AE~=0 and hence q = 1 that is work done is equal to the heat absorbed. in an isolated system neither heat nor work is exchanged and hence the total energy of the system remains unchanged, There is no transfer of mass also in an isolated system and hence both mass and energy remain unaltered. An isolated system does not do any work or work cannot be done on the system, In an open systeny; matter, heat and work can be exchanged between the system and its surroundings. 1.3.1 Enthalpy-heat change in chemical systems Chemical reactions are always accompanied by heat changes and the reactions are classified into two categories on the basis of whether heat is evolved or absorbed. Reactions in which heat is absorbed are called endothermic and those in which heat is evolved are called exothermic. Reactions are carried out either in closed vessels at constant volume or open to atmosphere at constant pressure. For reactions occurring at constant volume and considering the work to be only of pressure-volume work, the first law of thermodynamics may be written as dE » bg ~ Pd (1.9) Since dV’ = 0 no mechanical work is done and dw = 0. Hence for reactions taking place at constant volume the heat exchanged between the system and its surroundings is a direct measure of the change in the internal energy of the system. aE = by (10)Thermodynamics 7 For reactions carried out at atmospheric pressure (constant pressure), and under the constraints that the pressure within the system is equal to the pressure of its surroundings and remains constant, and considering only expansion as work it may be written for a finite change AE=E,-E, =q-w =q- P(¥,-¥) aay where £, and £, are the internal energies of the final and initial states and V’, and V/, are the volumes of the final and initial states. Rearranging Eq. 1.11 gives p = (Eq + PV) -(E, + PY) (1.12) where g, is the heat transferred at constant pressure. Just as E, P and V are state functions (E+ PV) is also a state function and may be given as H=E+ PV (13) His called enthalpy (Gk. to warm in). So Eq, 1.12 may be written as 4, = Hz-H,= AH ala Thus a change in enthalpy és equal to the amount of heat absorbed or evolved for chemical reactions occurring at constant pressure. The relationship between the two state functions, total energy and enthalpy of a system may be deduced. For a system in which both the pressure and volume vary, the enthalpies of the final and the initial states and the total energies may be expressed as H,-H, Ey +P, - PV, (1.13) AH = AE + APY) (1.16) If pressure is constant then Eq. 1.16 becomes AH = AE+P.AV (1.17) = tPA (1.18) The heat absorbed at constant pressure is used for increasing the internal energy of the system as well as to do work of expansion while the heat absorbed at constant volume is used only for increasing the internal energy of the system and no work is done. Thus AH > AE. However, in a compression process AV is negative and hence AH < AE, For processes involving solids and liquids AV is negligibly small and hence AH ~ AE, In the case of reactions involving gases AV is appreciable and cannot be neglected. For example in a hypothetical reaction involving ideal gases at constant pressure represented by a stoichiometric equation as aA = bB—> C+ dD (E19) Using the ideal gas equation PY = nT (1.20) PAVI= PO pass POs” PORT pag P ORD PAV) = RT. An (21) where An is the change in the number of mols of gases, that is, the difference between the number of molecules of products and reactants as given in the stoichiometric equation. The enthalpy change for the above reaction may now be written as AH = AE+RTAn 1.3.2 Application of first law of thermodynamics A few of the applications of the first law of thermodynamics relevant to chemical systems are given in this section.Engineering Chemistry (i) Molar heat capacity (C) is the amount of heat required to raise the temperature of one mol of a substance by 1° C and may be expressed as the rate of change of heat with temperature C= 8q/AT for | mol of substance (1.23) From the first law of thermodynamics (Eq. 1.9) since dq = dé + PAV de + Pay 24 ar aa) Molar heat capacity varies with pressure as well as temperature and hence can be expressed at constant volume (C,) and at constant pressure (C,), At constant volume d¥= 0 and hence Eq, 1.24 may be written as (1.25) or in terms of partial differentials C, (1.26) ‘Thus molar heat capacity at constant volume is defined as the increase in the internal energy of the system per degree rise in temperature. At constant pressure Eq. 1.24 may be written as av G, P| 1.27) oar (=| azn r or) I 28 or in terms of partial differentials as C,, [= | + al + |, (1.28) Differentiating Eq. 1.13 with respect to temperature at constant pressure gives F i Tl, " Az, (129) Combining Eqs. 1.28 and 1.29 molar heat capacity at constant pressure is given as oH Cp| = 1.30) “| ar L “ For the liquids and solids AH ~ AF and hence G and C, are similar but are different for gases. For an ideal gas C,~C,=R (ii) Ideal gases have a simple equation of state as PY = n RT and application of the first law to ideal gases implies the calculation of changes in state functions of internal energy (AE) and enthalpy (AH) and path functions of heat exchanged (q) and work done (vs). The values of path functions depends on the path followed in the change of state. There are four different paths or process conditions through which a change of state can be effected in an ideal gas. These include (i) constant pressure or isobaric process (dP = 0), (ii) constant volume or isochorie process (dV = 0), (ii) constant temperature or isothermal process (d7"= 0) and (iv) adiabatic process (8q = 0). (i) Isobarie process: At constant pressure and a finite change in volume from ¥, to Vth total work can be given as w= PU, ¥,)= PAV aan‘Thermodynamics - 9 ‘The work w will be positive (work done by the gas) when V, > V, (expansion) and w is negative (work done on the gas) under compression. For one mol of an ideal gas PV = RT and hence w=R(I,-1) (1.32) The relationship between heat transferred at constant pressure g,, change in enthalpy AM’ and the molar heat capacity at constant pressure C;, may be expressed as AH 4,~C,(T;~T)) (taking C, to be constant in the temperature range) (1.33) Similarly AE = g,-w=C,(T-1)) (134) (ii) Isochoric process: At constant volume V, and dV’ = 0 the following relationships hold good 2 w= [Pav =o (135) i 4,7, (7,-T,) (C, remains a constant) (136) AE =q,-w=4,=C{T,-T,) (137) AH = AE + A(PY) = AE + RAD) (138) =C,(T,-T) + RU,-T) (139) (1, > T; since P, > P, and q, is negative) =6(1%)-T) (1.40) (iii) Isothermal process: Temperature remains constant at 7, and d7'= 0. The isothermal process may be considered as equivalent to expanding the gas isobarically and compressing it isochorically. The relevant equations for calculating the parameters are w=RTIn(V,V,) (since AE=Oandg=w) (1.41 a) = RT In (P/P,) (ald) AH = AE+RAT=0 (1.42) (iv) Adiabatic process: The system is thermally insulated and there is no exchange of heat between the system and its surroundings. Hence g = 0. we AE (1.43) If expansion occurs work is done by the system (-w) and heat is taken from the system, hence, the internal energy and temperature decrease. On the other hand, during compression, work is done on the system and hence internal energy and temperature increase. AE = CAT=C,(7,-1)) (1.44) AH = C,(7,-T)) (1.45) (iii) Thermochemistry involves the measurement and analysis of heat changes that accompany physical or chemical transformations in a calorimeter. The reaction vessel is surrounded by water in the calorimeter and it is assumed that any heat evolved during a reaction is used only to raise the temperature of water in the calorimeter and the increase in temperature AT is accurately measured, The heat absorbed in an endothermic change or liberated during an exothermic change is called the heat of reaction, Heat10 Engineering Chemistry of reaction at constant volume is equal to AE, Since most of the reactions occur at constant pressure the heat of reaction is usually expressed in terms of enthalpy change (AH) accompanying the reaction. The enthalpy of reaction (AH) is the difference between the enthalpies or heat contents of the products and reactants AH = peodvets 7 reactams (1.46) Heat changes accompanying the transformations, whether AE or AH, are expressed for one mol of the reactant, Depending on the nature of the physical or chemical transformation taking place the enthalpy change is designated appropriately. Thus heat of combustion (AM,) is the change in enthalpy when one mol of the substance is completely burnt in excess of oxygen. Heat of formation (AH) of a compound is the change in enthalpy when one mol of the compound is formed from its elements in their commonly occurring (or standard) states. It is assumed arbitrarily that the enthalpy of an element in its standard state is zero, the standard state being defined as the most stable physical form at one atmospheric pressure and temperature of 298 K. The enthalpy of formation of a compound is indicative of the stability of the compound. In general, the lower the enthalpy of formation of a compound the more is its stability because the stability of a compound is inversely proportional to its heat content (intrinsic energy). Thus the enthalpy of a stable compound is negative. that is, its energy content is less than the ‘sum of its constituent elements. On the other hand if enthalpy of formation of a compound is positive the compound is unstable, Other commonly encountered heat changes include the enthalpy of fusion (heat change accompanying when one mol of a substance is transformed from the solid to liquid state at its melting point), enthalpy of vaporisation (heat change accompanying when one mol of a substance is transformed from the liquid to vapour state at its boiling temperature), enthalpy of sublimation (heat change accompanying when one mol of a substance is transformed directly trom the solid to vapour state at a given temperature), enthalpy of neutralisation (heat change accompanying when one gram- equivalent of an acid in dilute aqueous solution is neutralised by one gram-equivalent of a base and vice - versa) and enthalpy of formation of chemical bond or bond energy. A direct consequence of the first law is the thermochemical law called Hess's law of constant heat summation. Itis based on the concept of state function according to which any finite change in a state function such as the E or H depends only the initial and final states of the system and not on the paths through which such changes are brought about. The law states: the total heat change in any chemical reaction is the same whether the reaction takes place in a single step or in several siages. For example, the formation of CO, may be considered to occur in a single step Cigraphite) + 0,(g) —> CO,(g); AH =~ 393.5 kd (147) Or in two steps involving the formation of CO in the first step which is converted to CO, in the second step as ‘C(graphite) + %4 O,(g) —> CO(g); AH = — 110.5 kd (1.48) CO(g) + 4 Og) —> CO,(g); AH =~ 283.0 (1.49) ‘Thus, the heat of formation of CO, from the elements is the same (-393.5 kJ) whether the formation occurs ina single step or in two steps. Thus Hess’ law is usefull for calculating the heat changes in chemical reactions. The effect of temperature on heat of a reaction is given by Kirchoff’s equation as AH = H,-H, (1.50) where Hp = ¥ H (products) and Hy = ¥ H (reactants). On differentiating the Eq. 1.50 with respect to temperature KirchofT’s equation is obtainedThermodynamics n (224) (2) (2) ws) or GE Or Jp - A similar equation can be written for the variation of AE with temperature. (iv) Bond energy or the heat of formation of a bond may be defined as the average amount of energy (enthalpy change) required to break one mol bonds in a gaseous molecule to form gaseous fragments, atoms, radicals etc. It is more appropriate to call bond energy as bond enthalpy as it is calculated from measurements at constant pressure and is different from bond dissociation energy which is defined as the energy required to break a given bond in a compound. The bond energy depends on the molecular environment. For example the energy required to break the H-OH bond in water is 119.95 kcal/mol (501.9 kJ/mol) while the energy required to break the O-H bond in hydroxyl radical is only 101.19 kcal/mol (423.4 kJ/mol). The sum of these values is the dissociation energy of water (221.14 kcal/mol = 925.25 kJ mol ') that is the energy required to break the two O-H bonds in water and hence the average bond energy for the O-H bond in water is (221.14/2)= 110.57 k.eal/mol (462.6 kI/mol). In the ease of polyatomic molecules of the type AB,, the average bond energy of A~B may be calculated by dividing the heat of formation of the compound with the number of bonds 7. Thus for CH, the average bond energy of C-H bond is the heat of formation divided by 4 = 397.4 /4 = 99.4 kcal/mol (415.9 kl/mol) The bond energy of a bond is almost the same, irrespective of the compound in which it is found. Chemical reactions involving the breaking of bonds in reactant molecules which are endothermic and making of bonds in the product molecules which are exothermic. The greater the energy required to break a bond the stronger is the bond. The net change in bond energy during a chemical reaction involving bond breaking and bond making represents the enthalpy change of the reaction. Thus, it is possible to calculate approximately the enthalpy change of a chemical reaction by considering the bond energies of the bonds that have been broken and of those which are formed. (¥) Explosions may be regarded as taking place under adiabatic conditions as they are too fast to allow for the transfer of heat into the surroundings. The heat evolved during the reaction is utilised in heating the products of the reaction. The maximum flame temperature and the maximum explosion temperature may be calculated on the basis of adiabatic conditions, Changes in the internal energy. AF and enthalpy AH are utilised for heating the reaction products to the final tethperature. The reaction is assumed to take place in two steps between the same temperatures of initial temperature 7, (298 K) and the final temperature T,, For the process at constant pressure, the final temperature is the flame temperature and at constant volume the final temperature is taken as the explosion temperature. The final temperature T, to which the products are heated is calculated using Kirchhoff’s equation, Assuming that C,, remains constant in the temperature range T, to T,, the flame temperature may be calculated from the equation. n= Cp The explosion temperature may similarly be calculated using AE and C, because explosion is considered as a constant volume process. (1.52) (vi) Joule-Thomson effect is of practical importance in the liquefaction of gases. An ideal gas has no intermolecular attraction and hence the product PY remains a constant at any given temperature at all pressures. When such a gas expands under adiabatic conditions into a vacuum, no heat is absarbed or evolved, no external work or work to separate the molecules has to be performed. Hence q = 0, w= 0 and AF = 0, However when a real gas under high pressure is allowed to expand into vacuum or2 Engineering Chemistry a low pressure region, the temperature of the gas decreases as noticed by Joule and Thomson (Lord Kelvin). This was attributed to the fact that work was done by the gas in overcoming the intermolecular attractive forces between the gas molecules at the expense of the kinetic energy (internal energy) resulting in the decrease of the temperature of the gas. 1.3.3 Limitations of the first law The first law specifies that energy of an isolated system remains constant and that one form of energy can be converted into another. It also states, that energy is neither created nor destroyed. However, the first law does not indicate whether such a conversion is feasible and if so to what extent. It is well known that water flows downhill and that heat flows from a hot body to a colder one till the two reach a common temperature. Such processes occur naturally without the aid of any external agency and are called spontaneous processes. The spontaneous process by which a system proceeds from a non- equilibrium state to an equilibrium state is also called an irreversible process. A system always exhibits a natural tendency to proceed towards equilibrium and on attaining equilibrium it does not return to its initial condition on its own unless disturbed by external agencies. Though from experience it is possible to predict the feasibility of the natural processes mentioned above, the first law does not provide any criterion to predict the feasibility. The lack of criterion to predict the feasibility of a physical or chemical Process is a limitation of the first law. Thus, on the basis of the first law we cannot predict whether a reaction will occur when two chemicals are mixed. The first law also establishes the relationship between the state functions of internal energy and enthalpy. Accordingly AF is the heat change occurring in a process at constant volume and AH is the heat change occurring at constant pressure. However it does not specify the direction of heat change or flow. Most of the spontaneous chemical reactions at constant pressure are exothermic, leading to a conclusion that a reaction would proceed in that direction in which AH < 0, However, many endothermic reactions in which AH > 0, also occur spontaneously (e.g., synthesis of ammonia or nitric oxide). Thus the first law is unable to predict the direction of heat flow. The first law establishes the relationship between heat and work and the conversion of heat to work. On the basis, that energy can neither be created nor destroyed but only transformed, one would expect that heat could be converted completely into mechanical work. The conversion of heat into useful mechanical work is industrially important. However, experience has shown it to be otherwise. Joule and Thomson concluded on the basis of their experiments regarding heat energy and mechanical work that by spending 4.18 joules of mechanical energy or work one can realise 1 calorie of heat. This is known as mechanical equivalent of heat. However, in the reverse direction 1 calorie of heat does not produce 4.18 joules of mechanical work and a part of the heat energy is lost to the surroundings. Thus 100 percent conversion of heat energy into mechanical work is not achieved. However the total energy is conserved when the mechanical work and the heat dissipated are taken into account. Camot’s theoretical treatment of a reversible heat engine showed that the conversion of thermal energy completely into work is not possible. A heat engine takes heat from a source, converts some of it into useful work and discards the rest to a sink and this operation is possible only if the source is at a higher temperature compared to the sink. The efficiency of a heat engine e, is given as Networkdone by thesystem(engine) heat absorbed by the engine wy (1.83)Thermodynamics 13 where w is the net work done by the engine and is equal to the difference between the heat absorbed by the engine from the source (q,) and the heat discarded to the sink (g,), ‘Camot's theoretical treatment also resulted in a statement that all reversible engines operating between the same two temperatures have the same efficiency. This efficiency is independent of the nature of the working substance and depends only on the quantities g, and q.. These limitations necessitated the introduction of another physical law, namely the second law of thermodynamics, based on experience. 1.4 The Second Law of Thermodynamics The second law of thermodynamics is based on the principle of asserting the impossibility of carrying out a process. The law has been stated in many ways. According to Kelvin and Planck in any process it is impossible to convert the heat absorbed from a reservoir completely into work. It means that only a fraction of heat can be converted into work and the rest of the thermal energy is unavailable for conversion. It also means that heat exchange with a single reservoir cannot be harnessed to do mechanical work. According to Clausius heat cannot by itself,low from a cold to a hot body (spontaneously) without the intervention of an external agency. 1.4.1 Entropy Absorption of heat by a system increases its en2rgy. Since heat energy is not an organised form of energy (unlike electrical, chemical or mechanical energy) it enhances the disorderly or random motion of atoms and molecules in a substance (system). In contrast mechanical work involves an orderly transformation of the system from one state to another. It is possible to convert the organised form of energy completely into heat energy. However, it is not possible to convert heat energy completely into mechanical work or any of the organised forms of energy. A portion of the heat energy is dissipated to the surroundings. The conversion of an organised form of energy into heat energy is always accompanied by an increase in the disorder of the system. ‘Anew thermodynamic function called entropy, which is a measure of disorder, becomes necessary to explain spontaneous processes. The term entropy (Gk. = change) was coined by Clausius and the second law of thermodynamics uses entropy to identify spontaneous changes without violating the principle of conservation as stated by the first law. Entropy is represented by the symbol S. Since entropy is a state function its values depend only on the initial and final states of the system and independent on the path of change. Entropy is expressed in units of joules per Kelvin (jK~') and since entropy is an extensive property it is expressed for one mol of the substance as molar entropy in jK-'mol-!, The change in entropy of the system AS is given as AS =4q,,/T (1.54) The second law of thermodynamics may also be stated in terms of entropy as the change in entropy of an isolated system is always positive when it undergoes a spontaneous process. All natural processes are spontaneous and irreversible and hence are accompanied by a net increase in entropy. Thus the entropy of the universe (an isolated system) increases with every change that occurs in nature. When the entropy of the universe reaches a maximum and an equilibrium is attained it will result in an entropic doom. Using these ideas Clausius put forth the first law of thermodynamics as ‘the energy of the universe is constant’ and that of second law as ‘the entropy of the universe tends always to a maximum’.4 Engineering Chemistry ———+ 1.4.2. Entropy changes in spontaneous processes ‘Thermodynamically irreversible processes are spontaneous and hence must be accompanied by an increase in entropy. The change in entropy of an isolated system AS,,.,, consisting of the system of imterest (AS) and its surroundings (AS,,,) is the sum of the AS + AS.,, and is always positive for spontaneous processes. AS ug) = AS + AS, 20 (1.55) 1.4.3 Entropy changes for a reversible process In reversible processes the system undergoing a change between two states, is in equilibrium with its surroundings at every infinitesimal change. The energy exchanged between the system and its surroundings in the form of +3q (heat absorbed by the system) is equal to ~6q,,, (heat dissipated to the surrounding) at a given temperature T and hence 45 = 0, /T (1.56) For a measurable or finite change in the system the change in entropy AS of the system is the integral of infinitesimal changes (%-S) Jeqvir (57) where S, and S, represent the entropies of the final and initial states of the system respectively. The entropy change of a system between two states can be determined by determining the heat necessary to take it along a reversible path, between the same two states. For a reversible process the heat exchanged as well as the work exchanged should be reversible and for a reversible cyclic process Lqu/T =O0rAS=0 (1.58) ‘The change AS, ,,.= 0 for a reversible process and AS for the system = 0 at equilibrium. For reversible adiabatic processes, dg is zero and hence AS is always zero. Reversible adiabatic processes are isoentropic, 1.4.4 Evaluation of entropy changes If the work involved in a reversible process is only P -V work, Sw,,,= PAV and TAS = 6g... Hence AE =TéS- Pav (1.59) Equation 1.59 is in terms of state functions only and is applicable to all changes of state reversible or irreversible. Entropy changes for ideal gases are given the following equations in terms of molar heat capacity, pressure/ volume and temperature. AS =n C,In(Ty7,) +n Rin (VV) (1.60) AS = nC, In (TyT,)~n Rin (PyP,) (61) Entropy changes for phase transitions at constant pressure is given by AS = MHIT (1.62) The variation of entropy with temperature at constant pressure is given in terms of molar heat capacity and temperature asThermodynamics 15 (as), and for constant volume process (AS), = nC,In T/T, (1.64) ‘The AS thus depends on the ratio of temperatures and not on their actual magnitudes. Cn t/T, (1.63) 1.5 Equilibrium and Spontaneity Entropy is the basic concept which predicts the direction of a spontaneous process. In the case of isolated systems entropy of the system and its surroundings are considered together. However, many reactions are carried out at constant temperature, pressure or volume and in the case of such non-isolated systems which may be open, or closed, a change in spontaneity may be predicted on the basis of two alternatives: (i) by evaluating the MSouay = AS + AS. Three possibilities arise AS,,,,,> 0 for spontaneous reactions; AS,,,,~ 0 for reversible or equilibrium processes and AS,..., < 0 for non-spontaneous reactions. It is possible that AS<0 but, AS... > 0. (ii) The second approach is to consider the system alone and define the conditions of spontaneity and equilibrium, When a closed system alone is in thermal equilibrium with its surroundings at temperature T is considered, the change in entropy of the system, AS 0 at equilibrium. When a reversible change occurs in the system, transfer of heat occurs between the system and its surroundings such that AS=q,/T oF (AS~qulT)=0 However for an irreversible change (AS — q/T) > 0. If the process is carried out at constant volume and no work is done (q = 0) then AS~(AE/T) 2 0 or TAS - AE >0 or TAS> AE (1.65) Considering the system alone in the absence of any change in the intemal energy or volume, a spontaneous transformation results in an increase in entropy and hence entropy can be used as a criterion for spontaneity of transformation. If the temperature is kept constant, instead of the internal energy, the entropy change at equilibrium may not be zero. This may be explained with an example of liquid water and water vapour at equilibrium. They have different molar entropies and hence, AS is not zero. This is due to the fact that when water evaporates even at a constant temperature, the latent heat of -vapourisation is absorbed leading to an increase in the entropy of the water vapour. The internal energy also increases on vaporisation. ‘Thus for the system at constant T and V, (di = 0; d7~ 0) it may be written for an isothermal change (TS) — d(E)2 0 or-d(E ~ TS) > 0 or d(E — TS) <0 (1.66) The quantity (E ~ 7S) represents a difference between state functions and may be represented by a new state function A (German A = arbeit = work) called Helmholtz free energy or Helmholtz function or work fiunction so that A=(E~TS) (1.67) For a spontaneous process at constant T and V, Ad = AE-TAS (1.68)16 Engineering Chemistry and the change in work function Ad <0, for a reversible process at equilibrium it is zero. The equation implies that of the total amount of energy in a system only a part of it (AE — TAS) is available for work as the energy equal to TAS is stored in a disorderly manner and hence not available for doing work. For a thermodynamically reversible process taking place isothermally, Ad = AE-q,., (because AS =q,,/T) (1.69) According to first law of thermodynamics AE = 9. — Wy Of — Wa, = AE ~ dre, Substituting AA for (AE ~ q,,,) BA =~ Wy OF Wg =— AA (1.70) The decrease in the work function is equal to the maximum work that can be extracted from a system for an isothermal change between two states (at constant T and V), However, the work function is not used as a criterion of spontaneity because most transformations do not occur at constant volume. For a system undergoing change at constant temperature and constant pressure (47'= 0, dP = 0) it can be written that d(H-TS) <0 (1.71) The difference between the two state functions is represented by another state function G called Gibbs free energy or free energy given @s G=H-TS (1.72 a) =E+PY-TS (1.226) For a system undergoing spontaneous (irreversible) change at constant temperature and pressure AG <0. For changes under isothermal and isobaric conditions and for reversible changes AG = 0. Since most chemical transformations occur at constant temperature and pressure, spontaneity of the process can be determined using the change in free energy as a criterion. AG = AH-TAS (1.73) Since AH = AE + PAV we can write AG=AE+PAV-TAS or AG=AA+ PAV (1.74) Since — Ad = Way =AG = Wy PAV (1.75) It is clear that the decrease in free energy at constant temperature and pressure corresponds to the maximum work other than P-V work (expansion work) that can be performed by a system under reversible conditions. ‘The free energy depends on T and P and hence is conveniently expressed in terms of T and P as independent variables. dG = (6G/0P), dP + (6G/6T),, aT (1.76 a) Complete differentiation of Eq. 1.72 a gives dG = dH - TdS-SaT (0.76) But TdS = dE + Pd¥ (from Eq. 1.59) holds good for both reversible and irreversible processes. Further from Eq. 1.72 b H = E + PY and hence dif = dE + PdV + VAP. Substituting these into Eq, 1.76 b gives AG = dE + Pay + VaP — aE ~ Pav - SAT = VAP -SdT (177) Comparison of Eqs. 1.76 a and 1.77 shows thatThermodynamics 17 (Gin, =-S (1.78) and (6G/eP), = ¥ (1.79) From the above equations it is clear that G must increase with pressure at constant temperature and decrease with temperature at constant pressure. At constant temperature (isothermal change) d7'= 0 and hence Eq. 1.77 becomes dG = VP. The change in the free energy at constant temperature is obtained by integrating Eq. 1.79 between the initial and final pressures P, and P, jac = jrew (1.80) ii In the case of solids and liquids V can be considered to be constant as they are only slightly compressible. Jag=v fap or AG=VAP=¥(P,-P,) (1.81) i Free energy of pure solids and liquids are fairly constant over a wide range of pressures and hence changes in free energies are quite small. However, in the case of gases volume changes are quite appreciable with changes in pressures and hence changes in free energies are quite appreciable. For n mols of an ideal gas =n (R7/P) hence AG = RT In (PyP,) = ART In (V/V) (1.82) where V, and V, are the initial and final volumes respectively. 1.5.1. Standard free energies Free energy G being a state function, only the ctianges in the free energy AG are thermodynamically significant and can be manipulated by way of addition or subtraction in a manner similar to AH. The free energy change of chemical reactions AG is more important than the changes in work function AA because most of the reactions are carried out at constant pressure (usually one atmospheric pressure), The element in its stablest form at one atmospheric pressure at a specified temperature, usually 298 K, is considered to be in its standard state and the free energy Gog of the element in its standard state is assumed to be zero, The standard free energy of formation of a compound is defined as the free energy change accompanying the formation of a compound from the constituent elements, the reactants and products being in their respective standard states at a specified temperature. The standard free energy change of a reaction can be calculated from a knowledge of the AG? values of the reactants and products. Thus the free energy change of formation of a compound at constant temperature = (total molar free energy of the products ~ total molar free energy of the reactants). AG? = EG? (products)— ZG? (reactants) (1.83) Itis possible to predict whether a given transformation is feasible or not under standard conditions on the basis of the sign of AG? . When AG? is <0 itis indicative of a spontaneous reaction and conversely the reaction is non-spontaneous when AG? > 0 and AG} = 0 at equilibrium. ‘The criteria for a chemical reaction to occur spontaneously may be summarized as AG should be negative at a given temperature and pressure with both AH and AS making significant contributions. For AG to be negative AH must be negative and AS must be positive. In the case of exothermic reactionsAH will be negative and AG ~ AH and AS may be positive indicating spontaneity. However if the AS is negative the condition |AH| > |TAS| should be satisfied for spontaneity. In the case of endothermic reactions AH and AS will be positive but AG will be negative only when TAS> AH. 1.5.2 Gibbs-Helmholtz equation One can predict the feasibility of a chemical reaction only (298 K from the AG? values). Gibbs- Helmholtz equation is useful for predicting the feasibility of a reaction at other temperatures as it relates the variation of AG with temperature. The equation AG = AH ~ TAS (Eq. 1.73) itself is a simple form of Gibbs-Helmholtz equation. It states that AG is a function of T at constant pressure, Differentiating the above with respect to T (02) (0) (889), aT jp \ oT )p oT Jp oT )p (2) -7( 222) as assy a jp \ OF Ip Since (222) oT dp Substituting into Eq. 1.73 gives aowan+1( 2) (1.85) Equation 1.85 is another form of Gibbs-Helmholtz equation. Gibbs-Helmholtz equation can also be written in yet another form by differentiating AG/T with respect to T to arrive at AAG! ”) AH ( oT jp 7 This is yet another way of representing the variation of AG with T. (1.86) 1.6 Third Law of Thermodynamics It was shown that as temperature decreases AG approaches AH and at extremely low temperatures near absolute zero AG = AH. Nernst suggested that AG and AH approach equality asymptotically at temperatures close to absolute zero, Nernst heat theorem postulates that in the neighbourhood of absolute zero, all processes should occur without any change in the entropy and heat capacity. The entropy of a substance at any temperature must be greater than its value at absolute zero as S = 0 at T—> 0. Planck extended Nemst’s assumption by stating that re value of the entropy ofa pure solid or a pure liquid approaches zero at absolute zero. te Sp~Sy = [Lar (1.87) é T Lewis and Randall stated the third law of thermodynamics as every substance, element or compound has a finite positive entropy, but at the absolute zero of temperature, the entropy may become zero and does become so in the case of a perfectly crystalline substance. Eq. 1.87 may be written asThermodynamics 19 Jeoaar or ff fear (1.88) S,-in the above equation is called the third law entropy or absolute entropy. Ifthe pressure is one atm., then the entropy is also the standard entropy S°. The third law places a limitation on the value of entropy and also leads to the important conclusion of the impossibility of attaining absolute zero. 1.7 Thermodynamic Applications to Physical Equilibria For any pure substance in single phase of gas, liquid or solid, any variation in free energy is given by the Eq. 1.77 as dG = VAP - SAT. To have equilibrium in the phase, dG must be zero at constant T and P and the phase is said to be in equilibrium when the pressure and temperature are constant and uniform throughout the phase. For any pure substance undergoing change from one phase to another as in the case of one crystalline form changing to another crystalline form or melting of a solid or vapourisation of a liquid, the change in free energy for phase transition can be represented as, AG = G,-G, (1.89) where G, and G, are the molar free energies of the substance in the initial and final states respectively. If the two phases of the substance are in equilibrium and the pressure of the system is changed by dP, then the temperature of the system will have to change by dT in order to preserve the equilibrium. Since at equilibrium G, = G, and also dG, = dG,. But by Eq. 1.77, dG, = V,dP-S,AT and dG, = VAP - S47. Equating these expressions gives V,aP - S,aT = V, dP Sa (,~ V,) AP = (S,-S) aT dP/AT = AS/AV (1.90) where AS = (S, ~ 5,) the change in entropy and AV = (V; ~ ¥,) the change in volume for the process. The Eq. 1.90 is known as Clayperon equation. Since phase changes are reversible isothermal processes AS = AH/T (Eq. 1.62) where AH is the heat absorbed or enthalpy change per mol at the temperature T and is usually called the latent heat, L. For the phase transition solid to liquid AH = L,(latent heat of fusion) and similarly forthe transition liquid to vapour AH = Z, (latent heat of vvapourization) Equation 1.90 can be written as dPidT = LITAV (L91) In the case of phase transition solid to liquid AV = V;,~ V, and for liquid to vapour AV = V, - ¥, where ¥,, V, and V, are the molar volumes of the solid, liquid and vapour respectively. The more Useful (Clausius-Clayperon Equation (1.92) for calculating the latent heat of phase transformation is based on the following assumptions for liquid-vapour equilibrium (vapourisation) and solid-vapour equilibrium (sublimation). AV= ¥e- Vi~ V, since (V, >> V) and AV = V,—-V,~ ¥, since (V, >> vy) Assuming that the vapour behaves as an ideal gas V,= RT/P, Eq, 1.91 becomes dP/AT = L/TV, dP/AT = L P/RT?20 Engineering Chemistry \/P (4P/AT) = L/RT? or dln PAT = L/RT? (1.92) ‘Assuming that L remains constant over a small temperature change and integrating the above equation gives In PYP, = LR [(T,—~TyyT,T)) (4.93) where P, and P, are the vapour pressures at 7, and T, respectively. Itis possible to calculate the latent heat of transformation by using the above equation. 1.8 Thermodynamic Applications to Chemical Equilibria 1.8.1 Partial molar free energy (Chemical Potential) The derivations of various thermodynamic equations presented so far were based on the consideration of closed systems only as any change of state of the system was assumed to be due to changes in temperature or pressure. However in the case of open systems, the state functions change due to change in mass and composition also. Thermodynamic properties such as E, H, S, G, A, etc, are extensive properties because they depend not only P, Vand 7 but also on the mass or number of mols, 1 of cach constituent and composition of the mixture, The change in free energy dG, the most useful state function in chemistry, at constant T and P may be given in terms of the partial molar free energy G, and the number of mols of the component mas (4G), » = E, Gdn, (1.94) However if the temperature and pressure are not constant Eq. 1.77 becomes. (AG), » = VAP - SAT +, Gdn, (1.93) Gibbs called the partial molar free energy as chemical potential represented as jt (BGM) rp = ; and hence Eq, 1.95 may be written as (dG); » = VP ~SAT+¥, 4,4 n, 1.97) where the summation includes all the / constituents of the mixture. When small amount of substance i (dn, moles) is added to the system keeping all other variables constant, the change in free energy of the system is related to the composition of the system as given by , 4.96) (8G)p, p = Ley any, (1.98) The Eq. 1.98 is called Gibbs-Duhem equation. Other forms of Gibbs-Duhem Equation include G=S,ujn, 3 Lpnde,=0 (1,99 a) The chemical potential of each constituent is the contribution per mol of that constituent of the mixture towards the total free energy of the system at constant temperature and pressure. Its an intensive property of the system as it does not depend on the amount of the material but only its composition at constant temperature and pressure. For one mol of a pure substance (one-component system) the chemical potential is equal to the molar free energy (1 = G/n). The chemical potential is considered as the driving force behind a change. The concept of partial molar properties is useful to determine the properties of non-ideal mixtures. For example the total volume of «a solution of two components will be equal to the sum of the individual volumes V, and My only if the 4 and B form an ideal solution. InThermodynamics a general V4 V, + Vy. The increase in volume of the solution is calculated from the values of partial molar volumes and the number of mols of the components using the relationship dV =¥in, + Van, (1.99 b) ‘The variation of chemical potential of a component of a system as a function of temperature is related to partial molar entropy S, of the component as given by (OD p. 4 = — 5; (1.100) Since the entropy of a substance is always positive, the chemical potential would decrease with increase in temperature as given by the above equation, The variation of chemical potential as a function of temperature for solids, liquids and gases is shown in Figure 1.1. temperature Fig, 1.1 Variation of chemical potential with temperature. The chemical potentials of the solid and liquid phases of a substance are the same at the melting temperature 7,, and similarly the chemical potentials of the liquid and vapour phases remain the same at the boiling temperature 7, Similarly the variation of the chemical potential of a component i of a system with pressure is related to the partial molar volume ¥, of the component as given by (2 OP Ip, = — Mi (1401) 1.8.2 Van’t Hoff reaction isotherm and Van‘t Hoff equations Many chemical reactions do not go to a completion and may be considered as reversible reactions or equilibrium reactions. Chemical equilibria are dynamic and the rates of the forward and reverse reactions are the same at equilibrium. Chemical equilibria are also affected by changes in temperature, pressure and concentration of reactants. Guldberg and Waage proposed the law of mass action based on the effect of concentration on the rates of chemical reactions as “at a constant temperature, the velocity of a chemical reaction is proportional to the active masses of the reacting substances.” Guldberg and Waage assumed that active mass is equal to the partial pressures of the gases and concentration (expressed in moV/liter) in solutions. According to the law of mass action for a chemical equilibrium represented by aA +bB g—? cC + dD (1.102)2 Engineering Chemistry . the rate of the forward and reverse reactions vand v, are given respectively by v= k(AP(B}’ and v,=4, {CD}! (1.103) where k, and k, represent proportionality constants for the forward and reverse reactions and concentrations of the reactants and products are represented within square brackets, At equilibrium v= y, and x fron k (ArIBe The ratio k,/ k, is called the equilibrium constant K a constant at a given temperature, The equilibrium constant is also given as the ratio of the product of the concentrations of the products at equilibrium raised to powers corresponding to the appropriate stoichiometric coefficients, to the concentration of the reactants remaining at equilibrium raised to powers corresponding to their appropriate stoichiometric coefficients. Thus the equilibrium constant is governed by the ratio of the concentrations of the products to that of the reactants at a given temperature and is independent of the initial concentrations of the reactants. ‘Thermodynamic derivation of the expression for equilibrium constant is based on the condition that the free energy change accompanying the reaction at equilibrium must be equal to zero. The system at equilibrium is composed of several substances with varying compositions and hence the thermodynamic properties of the system must be expressed in terms of partial molar quantities The partial molar free energy, also called chemical potential 1 is related to dG at constant T and P by the Gibbs-Duhem Equation (1.98). The chemical potential of any constituent in any state may be expressed in terms of its activity a in that state as (1.104) w= O+RTIng (1.105) where 1° is called the standard chemical potential or chemical potential in the standard state of unit activity. The system at equilibrium may be considered as dn mol of each reactant gives rise to dn moles of each product. The concentrations of the reactants A and B diminish by adn and 6 dn moles respectively while the concentrations of the products C and D increase by c dn and dd moles respectively. The free energy change dG accompanying the process is given in terms of chemical potentials and may be written as chemical potential of the products — chemical potential of the reactants and represented based on Eq. 1.98 as (dG), p= Ludn = (ge dn * ty ddn)~(yadn+ py b dn) (1.106) At equilibrium (dG),, ,, = 0. Substituting for y in terms of u” and activities AG=0=[e (u2.+ RT Ina.) + d (ui, + RT Ina,)} [a (e+ RT In a,) + b (a+ RT In a,)] (1.107) < af ~ent+ anton boproarin| (1.108) a4ag 3. 4 AG=0=AG+ RTIn (2) (1.109) a4 ay‘Thermodynamics 2B «aft or =(AGIRT) = In (#4) (1.110) a4 4B ‘The left-hand side of the above equation is a constant. The ratio of the activities of the products and the reactants is also a constant at equilibrium for a given temperature and pressure and taking the term as equal to K, it may be written as AG® =~ RT In K or K= exp (—(AGYRT)) (Lu) where K is a thermodynamic equilibrium constant. The above relation holds good for all reversible reactions of all types involving gases, liquids and solids. In general the change in the free energy accompanying a reaction (Eq. 1.110) may be given as AG =AG°+RTINQ (L112 a) =-RTInK+ RTInQ (1.1126) The equation is called the van Hoff reaction isotherm. The thermodynamic equilibrium constant K is the ratio of the activities of the products and the reactants at equilibrium while Q (called reaction quotient) is the ratio of the activities of the products and the reactants at any state of the reaction. When AG=0, AG° =~ RT In Q and Q becomes K, the activities correspond to equilibrium activities, ‘The activities depend on the chosen standard state in which the reaction takes place. For reactions involving gases the standard state chosen is that of the ideal gas at one atm, pressure and the activity of the gas is related to its partial pressure. The equilibrium constant is expressed in terms of partial pressures and given the symbol K,,. In the case of liquid phase reactions, the standard state is chosen as the ideal solution of unit concentration (molarity or molality) and activities are related to molar concentrations. The equilibrium constant is expressed in terms of molar concentrations and given the symbol K,. Writing the Eq. 1.112 bas AG = RT In IK (1.113) it can be seen that AG depends only the ratio Q/K' as long as both are referred to the same standard state and independent of the particular standard state chosen. \Van’t Hoff reaction isotherm is useful in determining the feasibility of a reaction under a given set of conditions. Only when Q < K, AG < 0 and the reaction is spontaneous and when Q > K, AG > 0 and the reaction is not feasible under the chosen conditions of temperature, pressure or concentrations. However, the value of K may increase with temperature and at some temperature K > Q. The variation of the equilibrium constant K with temperature is expressed by van's Hoff equations. For reactions carried out at constant pressure the equation may be obtained by combining Eq. 1.11] and Gibbs-Helmholtz Equation (1.86). AG? =~ RT In K or in K=—AGURT (Bq. 1.111) Differentiating the above equation with respect to 7 dink = (EAN) ar J AH" represents the standard enthalpy change accompanying the reaction, Since AH does not vary much with pressure AH is taken to be approximately equal to AH”. Hence otMK _ AH (1s) oT RT?The equation is known as van t Hoff equation. On integrating the above equation another more useful form of the equation is obtained. ink = 2H + constant or log K= + constant (1.116) _ A 2303R7 A plot of log K against 1/7 gives a straight line with a slope of — (A#/2.303R). If the integration is carried out assuming AH to be constant between the temperatures T, and T, it is possible to calculate the equilibrium constant at T, if K is known at 7, using the Eq. 1.106 which is yet another form of van't Hoff equation. RT log (Ky/K,) = —(AH/2.303 n(24) 117) ih A similar equation called vant Hoff isochore is obtained for reactions carried out at constant volume. aink _ AE Pe (118) 1.9 Maxwell Relations Maxwell relations are mathematical expressions relating the different thermodynamic properties of a system to easily measurable physical quantities such as P, 7, V, etc. Maxwell relations are useful for interpreting physical properties of substances. Table 1.1 gives the various Maxwell relationships derived from the differential forms of fundamental thermodynamic expressions. Table 1.1. Maxwell relations Thermodynamic | Differential Independent ‘Maxwell relations functions ‘equations “variables. - : E de = Tas — PAV SandV (8T/0V), = —(@P/2S), | (A) Hu i= Tas + VAP Sand P (CT/EP),= (CV/0S), |B) A a4 =—SaT— Pav TandV OSIEV),= (PID, |(C) G 4G =~ SaT + VaP Tand P (vlan, =- (ese), | D) The expressions may be derived as follows: 1. Based on first and second laws dé = T'S ~ Pav (Eq, 1.59) Since E is a function of S and V the total differential equation for dif is written as dE = (GE 185), d5 + (CE/OV) A (119) On comparing the above two equations. we get (@EI@S), = T (1.120) and (GEIV), = -P (1.120) Differentiating the Eq. 1.120 a with respect to Vat constant S gives (Gl6V) ((@EIES), ], = CTV), (1.121 a)Trermodyamics . 25 and similarly differentiating Eq. 1.120 b with respect to S at constant V gives (G/aS) ((@EIAV),), = - GPS), (L121 b) But the left-hand sides of the above two equations are equal as £ is a state function Hence: (TOV), = — (CPI), (a 2. Maxwell's second relationship is obtained in a similar manner. Since H= E + PV dH = Tas + VaP (1.122) Since H is a function of S and P the total differential equation for d#/ is dH = (CHIOS), AS + (GHIGP), AP (1.123) Comparing the Eqs. 1.122 and 1.123 gives (GH/AS)p = T (1.124 a) and (GHiOP), = V (1.124) Differentiating Eq. 1.124 a with respect to P at constant S gives (GOP) ((CHIAS)p ]y = (CTIOP), (1.125 a) and on differentiating Eq. 1.124 b with respect to S at constant P gives : (2/88) [(GHIOP)s Jp = (@VIES)p (1.125 b) Since H is a state function and d# is an exact differential hence {PH/(@S OP) = [2 H/(OP 45)} ‘Comparing Eqs. 1.125 a and 1.125 b we get the second relationship of Maxwell as (OTIP), = (OV 105)p i) 3, Maxwell's third equation (C) is obtained from the variables T and Vas follows: dd =—SdT- Pav Atconstant V (6A/6T), = -S (1.126 a) and at constant T (CA/OV), = -P (1.126 b) Differentiating equation (1.126 a) with respect to V at constant 7'gives (iV) ((2A/0T),}, = —(ES/OV), Differentiating equation (1.126 b) with respect to T’at constant V gives (l0T) (CAV) ly = - CPT), (1.127 a) Since A is a point function the order of differentiation does not affect its properties. Hence the above second derivatives are equal (IBV) [(@A/AT),] = (WET) [(GALAV) ] (1.127 b) ‘Therefore (€SiV), = (@PIT), © 4, Equation 1.77 is dG= VaP-SaT At constant temperature d7"= 0 hence (dG),= VAP), oF (@G/EP), = V (1.128 a) At constant pressure dP = 0 and Eq, 1.77 simplifies to (4G), =-S(dT), oF (OG/T),=-S (1.128 b) On differentiating Eq. 1.128 a with respect to 7 at constant P gives (GIT) [(CGIAP),), = VIET)» (1.129)26 Engineering Chemistry Similarly differentiating Eq. 1.128 b with respect to P at constant T gives (G6 ) [(GGIST)p] = - (OSI0P), (1.129 b) Gisa state function and dG is an exact differential and hence Maxwell’s relation is (OVi0T)y = ~(OSIOP), Solved Examples 1, Calculate the (a) work done by 2.5 moles of a gas ‘under isothermal conditions at 30° C when it expands from 10 liters to 50 liters against an external pressure of f atm, and when it expands reversibly. Solutio (a) w= PAV= 1 atm, pr, * 101.3 j (40) = 4082 j tb) w= nRT in (V/V) = 2.5 mols * 8.314 j/deg/moles « (303 K) * (in 50/10) = 10135.76 J or 10.138 kJ 2. Calculate w, q and AE for 2 mols of. an ideal gas expanding from 10 at to 1 atm, reversibly under isothermal conditions (T = 25° C). Solution: w =n RT In (P/P3) and since AE=0,q=w) ‘2% 8314 x 298 x In (10/1) WALLT J = 14k M41 kg * 3. Calculate AE for the combustion of liquid benzene if the heat of reaction at constant pressure at 25° C was determined to be ~ 780.98 k.cal/mol Solution: CH) +7 40, —> 6 COMg) +3 HO (0); AH=780.98kcal — AE=AH-An RT =~ 780,98 cal ~ [(-1.5)*1.99 10° kcal. 298] = ~780.98 + 0.889 =— 780.09 kcal/mol 4. Calculate the AE for the oxidation | mol of hydrogen to yield | mol of liquid water, if the standard heat of formation of water is ~ 285.85 kJ/mol. Solution: Hg) + 0, (e)—> H,0() AE = Alf An RT = = 285.85 kJ —{(-1 4) « 8.314 = 109 ks = 298)] =~ 285.85 + 3.716 = — 282.13kI/mol () 3. Calculate the enthalpy change when 50 g of water is heated from 30°C to 45°C at one atmospheric pressure. Assume the molar heat capacity remains constant in the temperature range at 18,1 cal/K/mol Solution: AHl= oC {T,—7)) (50/18) * 18.1 cal/K/mol * (343 - 328) 2.78 * 18.1 « 15 = 754.8 cal/mol . 6. Calculate the heat of formation of water at 100" C, if the standard heat of formation of water vapour is ~ 241.83 KI and the molar heat capacities of hydrogen, ‘oxygen and water vapour are assumed to remain the same in the tempersture range at 29.0, 29.16 and 36.4 J/deg mol. Solution: Enthalpies at two different temperatures are related to the difference in mean molar heat capacities of products and reactants (AC, = C, (products) ~ G, (reactants)) pe » as given by the equation AH (at T,)~AH (at T,) =A, (T,~7)). Hyg) + 40, (g)—> H,0 (g); AH? (at 298 K) = 241.83 kJ AC. 16.4 — (29.0 + 4 * 29.16) 7.18 « 107 ki/deg AH} (at 373 K) = AH? (at 298 K) + AC, (373-298) =~ 241.83 + (-7.18%103 * 75) = 242.37 kJ/mol 7. Calculate the standard heat of formation AH? of Propane from its elements if AH for combustion of propane is~$30.6k.cal/mol at 25°C and AH} forCO, and H,O (/) ate — 94.05 and ~ 68,32 kcal respectively.Solution: C,H,(g) + $0,(g) —> 3 COAg) + 4 H,0(D; AH=~5306 kcal AHP (propane) =[3 (AH? (CO,) +4 AH? (H,0)) ~ AH (combustion) = [3 (94.05) + 4 (-68.32)] - (-$30.6) + ~ $55.43 + 530.6 = 24,83 k.cal/mol & Calculate the enthalpy of change at 25° C for the reaction H,C=CH,(g) + Hg) —> CH, from the available bond enthalpy (energy) data of H-H = 104 keal, C-C = 83 keal, C-H = 99 kal ~ (Al ¢_ct 2AH ey) * (AH eae + AH (83 + 98) + (1474104) =—30 kcal . 9. Calculate the heat of formation of CO at constant pressure if the heat of formation at constant volume at 30° C is 28.6 k.cal/mol Solution: Cl) + 40, —> C0 (@): AE = 28.6 kcal; An=1-1/2=1/2 AH =AE+ An RT = 28.6 * 10° cal « 14 « 1.99 = 303 = 288.98 k.cal/mol 10. The free energy change AG for a reaction is found to be -3.138 kcal at 300 K and (@ (AGV0 7) is ~14.39 cal/deg. Find AH for the reaction at 300 K. Solution: From Gibbs-Helmholtz equation AAG) ar }p == 3138 - 300 (-14.39) 3138 +4317 =+ 1179 cal = + 1.179 kcal aweao-1[ . 11. The equilibrium constant for the reaction N,+ 3H, @—> 2 NH, is 1.64 « 104 atm, at 400°C and 0.144 « 104 at ‘500° C respectively. Calculate the heat of formation of 1 mol of ammonia from its elements within the given temperature range. Thermodynamics 27 te | =~ {AH(2.303 * 8.314)] Solution: log (K/K,) = ~ (AH / 2.303 R) ( , 1.64x10~ °F o.144x104 (100/673 * 773) 1.0565 = ~ AH/(19.147) « 1.922 « 104 AH =~ 105.25 ki/2 mol or ~ 52.6 kJ/mol 12. Equilibrium constant for a reaction is 10,000 at 25°C. Calculate AG for the reaction, Solution: AG =—RTInK 1.99 * 298 « In 10,000 =~ 5461.7 eal + 13, Calculate the entropy increase in the evaporation of one mol of water at 100° C. The latent heat of vaporisation of water at 100° C is $40 cal/g. Solution: Since latent heat of vapourization = Gey = 540 cal’g * 18 g/mol = 9720 cal/mot AS = q.,/T = 9720/3973 = 26.06 camovK 14, Gibbs free energy change for a reaction at 300 K and. 310 K are ~29kcal and —29.5 k.cal respectively. ‘Determine AH and AS at 300 K. Solution: AS = [0 AGICT] AG 5y 7-7 10 =~ 50 cal/deg AH =AG + TAS =—29,000 + (50 « 300) =~ 14,000cal = 0 K.cal. . 15. Calculate the entropy change when 100 g of solid ice is. transformed to liquid water at 0° Cand | atm. pressure. The latent heat of fusion is 79.92 cal/g. Solution: AS= AHIT (since g,,, = AH at constant pressure and siven temperature) = (79.92 x 100)273 = 29.27 eaviK.Engineering Chemistry 16. Calculate the entropy change when 5 mols ofan ideal Solution: gas expands isothermally and reversibly to 3 times its AS=n G, In (TyT,)~n Rin (PP) initial volume. C2 C, ERAS Solution: = 5% 2.5 «8314 x In (233/263)— 5 * 8314 AS= nC, In(TyT,) +n Rin (VV) xin (15/5) 045% 83 14% In25=381 SK =~ 12.575 ~(-$0.05) = 37.475 J/K/mol . . 17, Calculate AS when an ideal gas undergoes a change from its initial temperature of ~10°C at 5 atm.pressure to ~ 40° C and 1.5 atm. pressure. (For one mol of an ideal gas C,= 1.5 R). Review Questions >" 1. Explain the terms system, surroundings and boundaries. 2. What are the different types of processes by which a system changes from one state to another. 3. Explain the term state function. Give examples. 4. Distinguish between extensive and intensive properties. 5. How is the absolute scale of temperature arrived at? 6. What are reversible and irreversible processes? 7, How are heat, work and energy related? 8. State the first law of thermodynamics and explain its significance. 9. ‘What are the heat changes that occur in chemical systems? 10. What is the meaning of enthalpy? How is it expressed? 11. Explaia the term molar heat capacity? How does it vary with pressure and temperature? 12, Write a note on the application of first law of thermodynamics to an ideal gas. 13. State Hess’s law of constant heat summation, How is it useful? 14. What is bond energy? 15. What are the limitations of the first law of thermoxtynamics? 16. State the second law of thermodynamics and its significance. 17. Explain the term entropy. How does it change in reversible and irreversible processes? 18. State the thermodynamic eriteria for spontaneous process st constant temperature and constant pressure 19. What is work function? How is it related to entropy? 20. Derive the Gibbs-Helmboltz equation. What are its apptications? 21. How is the entropy change expressed in terms of P and T of the system? 22, What is absolute entropy’? 23. Derive the Clayperon and Clausius-Clayperon equations, What is their use? 24, Derive an expression for the variation of equilibrium constant of a reaction with temperature. 25. What are Maxwell relations? Derive any one relation, 26. Explain the term chemical potential. How does it vary with temperature and pressure?PHASE RULE 2.1 Phase Equilibrium Phase equilibrium is said to exist when two or more phases coexist in a heterogeneous system. Such a heterogeneous system is conveniently studied on the basis of thermodynamic considerations by a generalisation called Piase rule deduced by J. Willard Gibbs (1876). The effects of temperature, pressure and concentration of the constituents on the heterogeneous equilibrium may be predicted quantitatively with the help of a phase diagram. 2.2 Definitions The terminology used in phase rule needs definition. Accordingly a phase is a homogeneous and physically distinct portion of a system separated from other parts of the system by definite boundaries. ‘The phase can be separated by mechanical operations such as decantation, sedimentation, filtration ete., which are carried out without affecting the temperature, pressure or composition of the system. Separation methods such as evaporation, distillation, adsorption or extraction are not included as they interfere with the temperature, pressure or composition of the system. Phase rule is concerned with the existence or non-existence of a phase under a given set of conditions. Since gases are readily miscible in all proportions a mixture of gases such as air constitutes a single phase. In the case of liquids the number of phases present depends on the miscibility of the liquids. A liquid layer is considered as a single phase as long as it is homogeneous irrespective of whether it is a pure substance or a mixture of a number of miscible liquids. When two liquids are immiscible and a surface of separation exists between them the system consists of two phases. Each solid constitutes a separate phase. Each crystalline phase of 2 polymorphic solid or allotropic form of an element is a separate phase with distinct boundaries (e.g., rhombic sulphur and monoclinic sulphur). A solid solution on the other hand is homogeneous irrespective of the number of solids and hence constitutes a single phase. Component of a system is an independent chemical constituent and the number of components of a system at equilibrium is the smallest number of independently variable chemical constituents by which the composition of each phase can be expressed directly or in the form of a chemical equation, For example the ice-water-water vapour system consists of three phases but all the phases can be represented by asingle chemical component, namely, HO. Hence this system is a one-component system. In writing of chemical equations the use of +, — or 0 as coefficients is permissible. The number of components in a given system at equilibrium is also equal to the difference between the number of chemical species and the number of equations relating to the concentrations of these substances at equilibrium. Thus the decomposition of calcium carbonate as represented by the following equilibrium consists of three phases, CaCO, (s) = CaO (8) + CO, (g) (1) solid CaCO,, solid CaO and gaseous CO, but the number of components is only two because each30 Engineering Chemistry - + of three phases can be described in terms of any of the two components as given by the following equations. Phase Components CaOandCO, or CaCO,andCa0_ or CaCO, and CO, CaCO, = C20+CO, or = CaC0,+ C20 or=— CaCO, +0 CO, 22) CaO = Ca0+0CO, or OCAaCO,+CAO or ~—CaCO,- CO, 3) CO, =0Ca0+CO, or CaCO,-Cad_ or_~— CaCO, + CO, (24) 2.3 Gibbs’ Phase Rule The number of degrees of freedom, F, is related to the number of phases P and the number of components Cin a heterogeneous system existing in equilibrium. The relationship is expressed as given by 2.5 and is known as phase rule. F=C-P+2 (2.5) The term degrees of freedom or variance refers to the minimum number of independently variable factors, such as temperature, pressure and composition of phases that must be specified in order to describe the conditions of a system. For example when liquid water, solid ice and water vapour coexist in equilibrium the degrees of freedom F'= 0 and the system is said to be invariant or non-variant as the three phases can coexist only at particular temperature and pressure which are automatically specified. When only two phases of the same system coexist the degree of freedom F = 1 and either temperature or pressure has to be specified. 2.4 Application of Phase Rule to One-Component Systems One-component systems include the water system and the sulphur system. For a one-component system the degrees of freedom to be specified at equilibrium is given by phase rule as F=C-P+2=(1+2)-P=3-P. Three different possibilities arise depending on the number of phases existing and the number of degrees of freedom to be specified will be (i) F = 2 when P= | (bivariant system), (ii) F= | when P= 2 (univariant system) and (iii) F= 0 when P= 3 (invariant system). Thus for a one-component system the maxintum number of degrees of freedom is two and hence such a system can be completely represented by atwo-dimensional diagram, Temperature and pressure are the most convenient variables (degrees of freedom) to describe the equilibrium conditions of one-component systems. The important parts of such phase diagrams include (i) area (ii) boundary line or curve and (iii) point. Areas represent a bivariant system while lines and point represent the univariant and invariant systems respectively. These aspects are described with the help of phase diagrams for water and sulphur systems. 2.4.1. Water system The phase diagram for the water system exis is shown in Figure 2.1, ing in three phases, namely, solid, liquid and vapour phasesPhase Rule 31 ~ Simei annem critical pressure 1/ aw 218 atm melting curve vapourisation curve triple point critical temperature -273 0 100374 temperature (*C) Fig, 2.1. Phase diagram of ice-water-water vapour system There are three areas in the phase diagram as represented by AOB, AOC and BOC. Only one phase exists in each of these areas, namely, water vapour in AOB, liquid water in AOC and solid ice in BOC. In the area F=1 ~ | +2 = 2. It is necessary to specify both temperature and pressure coordinates to locate any point within these single-phase areas. The boundary lines are 04, OB and OC representing the existence of two phases in equilibrium. The line OA is called the vapour pressure curve. Along the line Od liquid water and water vapour coexist and the phase rule requires that any one degree of freedom or variable is to be specified, to locate a point along the line, The degrees of freedom are given as F = | - 2 +2= 1. If the temperature is specified, the other variable namely, pressure automatically gets fixed. Thus at any specified temperature there is only one pressure at which water vapour is in equilibrium with liquid water, Similarly, at any specified pressure there is only one temperature at which the two phases coexist. The line OA has the upper limit at 374° C which is called the critical point. Above the critical temperature, the liquid phase merges with the vapour phase and the two phases cannot be distinguished from each other. Line OB is the sublimation curve of ice and represents the coexistence of water vapour and solid ice. The point B at ~273° C represents the merging of the two phases. The line OC is the melting curve of ice and represents the coexistence of solid ice and liquid water at equilibrium. The line slopes towards the pressure axis indicating that the melting temperature of ice decreases with increasing pressure. The triple point O is the meeting point of the three curves OA, OB and OC where all the three phases—solid ice, liquid water and water vapour coexist. The experimentally determined triple corresponds to a temperature of + 0,0098° C and a pressure of 4.58 mm of Hg and represents an invariant system since there is no degree of freedom, F= | —3 + 2 = 0. Even a slight variation of temperature ot pressure from the specified values will cause the disappearance of one of the phases. The curve OA’ represents the equilibrium between the supercooled liquid—a metastable phase and solid ice, Normally liquid water solidifies at 0° C at one atmospheric pressure. However, it is possible to supercool clean liquid water free from any dust to several degrees below 0° C. The curve O4” is thus32 Engineering Chemistry the vapour pressure curve of the supercooled water and vapour pressure of supercooled water is higher than that of ice. The metastable phase changes to the thermodynamically stable phase of ice even from a slight disturbance or the introduction of a crystal of ice as seed. ‘The practical application of phase rule for water system can be understood by considering the phase changes that occur along the lines xyz and pgr. At the point x the only phase that can exist is ice and with increasing temperature along the line xyz ice melts at the point y on the curve OC, and at the point z only liquid water can exist. Similarly at a lower pressure along the line pgr, the point p represents the existence of only one phase namely, ice which with increasing temperature changes into the vapour phase directly (sublimation) at the point g on the curve OB, and at the point r only the vapour phase exists. The principle of sublimation is of importance in freeze drying of thermally labile (unstable) products such as food, biological and pharmaceutical products which may decompose if dehydration by evaporation or drying at higher temperatures at atmospheric pressure is adopted. Freeze drying involves reducing the water content in the product (dehydration) by freezing it to solid ice at a low pressure of about | mm of Hg and then subliming ice to vapour at the same pressure so that it escapes from the product. The principle of sublimation is also used in the case of dry ice (solid carbon dioxide) used as a refrigerant. Sublimation of a solid occurs if it is heated under conditions such that, the partial vapour pressure is less than the triple point pressure. For solid carbon dioxide the triple point pressure is 5.11 atm. and hence the solid can be sublimed at one atmospheric pressure with the temperature remaining constant at ~ 78.5° C. Similarly iodine with a critical triple point temperature of 114° C and pressure of 90 mm of Hg sublimes into vapour at ambient temperatures because the partial vapour pressure is less than 90 mm even though the atmospheric pressure is 760 mm. However, solid iodine can be melted into a liquid by heating in a closed vessel. 2.4.2 Sulphur system Polymorphism (allotropism in the case of elements) refers to the phenomenon of a solid substance exhibiting more than one crystalline phase each with a distinct melting point and physical properties. Sulphur exists in two polymorphic forms, the rhombic (S,) and the monoclinic (S,,) form. In addition sulphur also exists in the melt (liquid) and vapour phase. However, for a single component system the maximum number of phases that can coexist is only three and hence all the four phases (two solid, one liquid and one vapour phase) cannot coexist. The phase diagram of the sulphur system is shown in the Figure 2.2. E, solid (5) liquid pressure temperature Fig. 2.2: Phase diagram of the sulphur systemPhase Rule 33 ‘The phase diagram shows four areas ABCD, DCEF, ABEF and BCE. The area below ABCD represents the region where only sulphur vapour exists, The region to the right of DCEF has only one phase namely, liquid sulphur. The area to the left of ABEF is the region where solid rhombic sulphur exists while the area enclosed within BCE solid monoctinic sulphur alone exists. The areas represent a bivariant system and hence both temperature and pressure must be specified to define the condition of any point within the given area. The boundary lines AB, BC, CD, BE, CE and EF separating the various areas represent the univariant systems. The number of degrees of freedom to be specified is 1, either temperature or pressure is to be specified. (F = 3-2= 1). There are four metastable curves shown in dotted lines BG, CG, EG and BB’ in the Figure 2.2. The line or curve AB extends between $0° C and 95.6° C and represents the vapour pressure curve of 5, The vapour pressure is not measurable below 50° C and above 95.6” C S. transforms into S,, Thus the point B represents the éransition cemperature for Sq1o Sy- Rhombic sulphur on rapid heating, melts to liquid sulphur at 115° C (point G) without going through the transition to S$, The curve BG represents the metastable sublimation curve of rhombic sulphur. The boundary line BC represents the vapour pressure curve of monoclinic sulphur and its melting at 120° C to give liquid sulphur. The curve CD is the vapour pressure curve of liquid sulphur while the curve CG represents the metastable vapour pressure curve of the supercooled liquid sulphur. The line BE is the transition of rhombic sulphur to the monoclinic sulphur. The line is sloping away from the pressure axis indicating that the transition temperature for the Sto S,, increases with an increase in pressure. This is due to the fact that the denser phase of rhombic sulphur is relatively more stable compared to the lesser dense phase of monoclinic sulphur, as pressure increases. Since the formation of rhombic sulphur is accompanied by liberation of heat the transition temperature increases with increasing pressure. The line CE separates the monoclinic sulphur and the liquid sulphur and slopes to the right as density of the liquid phase is lesser. The line EF represents the melting of the rhombic sulphur to a liquid. The dotted line EG represents the metastable vapour pressure curve of the super cooledmonoclinic sulphur. The dotted line BB" represents the metastable vapour pressure curve of monoclinic sulphur. The sullphur system also exhibits four triple points, B, C, E and G, the last one~G being a metastable one. At the triple point three phases coexist and hence the system is invariant with no degrees of freedom. Hf any of the conditions are changed one of phases will disappear. The phases at equilibrium at the triple points are as follows: B — (95.6° Cand 0.006 mm ) ~ equilibrium of S,, S,, and sulphur vapour C ~ (120° C and 0.04 mm) — equilibrium of S,,, liquid sulphur and sulphur vapour £ — (151° C and 1288 atm) — equilibrium of S, S,,, and liquid sulphur At the metastable triple point G (115° C and 0.03 mm) the three phases that coexist are rhombic sulphur, liquid sulpur and sulphur vapour 2.5 Phase Rule for Two Component Systems According to the phase rule for a two component system the maximum number of phases that can exist will be four; P= C— F +2 = 2-0 + 2=4, The degrees of freedom will be zero for a two component four phase system. The maximum number of degrees of freedom will be 3 if the two component system exists in a single phase; F = C - P + 2 = 2-1 +2 = 3. The three degrees of freedom have to be temperature, pressure and composition. The phase diagram requires a three-dimensional representation.4 Engineering Chemistry However, in the case of solids such as alloys the vapour phase does not exist and hence the effect of pressure is negligibly small on the equilibrium. Experiments are carried out at atmospheric pressure (constant pressure) and the condensed or the reduced phase rule equation of F = C~ P+ 1 is sufficient to describe such condensed systems in which the vapour phase is not considered. The condensed phase rule thus relies only on two variables, namely, temperature and composition. The phase diagrams are called temperature-composition diagrams. These diagrams are obtained by thermal analysis. 2.5.1. Thermal analysis The method involves the study of the heating curves, or more commonly the cooling curves (time- temperature relationships). The heating and cooling curve of a solid sample undergoing melting is shown in Figure 2.3. ‘melting point temperature temperature time > time (a) beating curve (b) cooling curve Fig. 2.3 Heating and coolirig Curves of a solid undergoing melting When a pure solid is heated slowly (~ 1° C/min) the temperature increases linearly with time until the solid starts melting. During the transition of the solid to the liquid phase the heat supplied is utilised to bring about the phase change (latent heat of fusion) and the temperature remains constant for a period of time till all of the solid is completely changed to liquid as indicated by the plateau in the heating curve. Once melting is completed the temperature increases again linearly with time. The temperature of the molten soli its pure state on slow cooling (~1° C/min) decreases linearly with time till the freezing point is reached and the solid makes its appearance. The temperature remains constant over a period of time till all of the liquid is transformed into the solid phase giving rise to the plateau region in the cooling curve. After complete solidification the temperature decreases continuously with time, Similar heating and cooling curves are obtained for phase transitions between crystalline phases of a solid and the freezing of mixtures of solids of known composition. 2.6 Application of Phase Rule for Two Component Metal (Alloy) Systems ‘The behaviour of two component systems is of importance in engineering and may be studied conveniently under the following types, namely, (i) substitutional solid solutions, (ii) formation of a simple eutectic (ii) compound formation with a congruent melting point and with an incongruent melting point, (iv) partially miscible solids and (v) interstitial solid solutions.Phase Rule 35 2.7 Substitutional Solid Solutions ‘Substitutional solid solutions are obtained when one solid dissolves in another completely to form a homogeneous mixture. The solute atoms substitute for solvent atoms in the crystal lattice of the solvent. Substitutional solid solutions of unlimited solubility are formed by two elements having the same number of valence electrons, the same crystal structure and when their atomic radii of are almost the same or differ by less than 8%. Copper-nickel alloy system is an example of substitutional solid solution. 2.7.1 Copper-nickel alloy system The phase diagram of copper-nickel system is shown in the Figure 2.4. The two elements are soluble in each other over the entire range of compositions. A homogeneous solid solution is a single phase and hence the system has a maximum of 2 phases, a solid and a liquid. The freezing points of pure copper and nickel are 1083° C and 1452° C respectively. The addition of nickel to copper raises the freezing point, while the addition of copper to nickel decreases the freezing point and hence the freezing point of a mixture of copper and nickel of any composition lies between the individual freezing points of the metals. The upper and the lower curves in the diagram represent the liquidus (freezing curve) and the solidus (melting curve) respectively. Only one phase namely, the liquid phase exists above the liquidus while the solid phase alone exists below the solidus curve. In between these two curves both solid and iquid phases coexist with both the components forming a continuous series of liquid and solid solutions in equilibrium, the composition being determined by tie lines. temperature eo (183°C) solid solution time wt % of nickel 19 Fig. 2.4 (a) Cooling curve and (b) temperature-composition diagram of copper-nickel system ‘The number of phases at the point p is one (liquid phase) and hence for two component single phase system, the number of degrees of freedom is 2. Both temperature and composition have to be specified to describe the point. Cooling the liquid at point p to temperature 71 results in the separation of the solid and the system becomes a two phase system with one degree of freedom. The compositions of the liquid phase and the solid phase at a temperature of 71 are given by points a and 6 respectively. Further cooling changes the composition also. The solid formed is neither pure copper nor pure nickel but a% Engineering Chemistry solid solution of nickel in copper. At point ¢ the system consists of a liquid of composition given by point a on the liquidus curve in equilibrium with the solid solution whose composition is given by the point b. The dotted line acd is called the tie line. The relative proportions of the two phases at the point cis given by lever rule, according to which Amount of Solid _ ac ‘Amount of Liquid — be ‘The solid of composition b that separates out may be melted separately to a give a liquid of composition 4 which on cooling to a temperature corresponding to d gives out a solid solution of composition e. It can be seen that the solid solution of composition e is richer in nickel compared to that of the solid solution of composition b. The procedure may be repeated to get ultimately pure nickel. This process of separation of a mixture into its pure components is called fractional crystallization and forms the basis of zone melting or zone refining 2.7.2. Zone refining Zone refining is used extensively for the preparation of highly pure metals required for the electronic industries and actually involves carrying out fractional crystallisation repeatedly. 4 furnace is passed from one end (A in the Figure 2.5) to the other end (B) of a long uniform bar of the solid to be purified at a slow rate in the range of 3-¢ em/hour, The furnace on reaching the end B is quickly brought to the end 4 for the second pass of the furnace. The passage of the furnace from A to B is repeated several times. 4 liquid zone is formed as the solid melts and the moving liquid zone melts the solid in front of it. Solid crystallises out behind the moving zone. The impurity distributes itself between the solid and liquid phases such that the ratio of the concentrations of the impurity in the two phases is a constant K at a given temperature, The constant is called the segregation constant ot partition constant, The value of K< | for impurities which depress the freezing point and K >I one for those which increase the freezing point. moving Fame resolidified molten solid to be purified portion zone Fig. 2.5 Representation of zone refining If K < | the liquid contains more impurity, while the solid crystallising out of the liquid has lesser impurity. The passage of the zone along the bar leads to an increase in the concentration of the impurity in the liquid and since K is a constant the concentration of the impurity in the solid crystallising out also increases proportionately. The moving zone thus sweeps all the impurities along the bar towards the end B. It has been shown that for K values in the range 0.1-0.5 about 20 zone passes will produce an extremely pure metal at the end A. ‘The segregation constant K >I for impurities which elevate the freezing point. In such cases the impurities tend to remain in the solid phase and with multiple passes of the furnace the impurity accumulates at the end A._ Phase Rule a 37 2.8 Eutectic Forming Systems ‘When two metals are completely miscible in the liquid state but do not have any solid-solid solubility, the phase diagram consists of two solubility curves intersecting at a point called the eutectic point which is characterised by the temperature called eutectic ‘emperature and a composition called eutectic composition. Eutectic (Gk = easily melting) point has a unique composition in that it has the lowest melting point. Eutectic temperature is the lowest or minimum temperature at which the liquid phase can exist. Two component alloys such as bismuth-cadmium, lead-silver, copper-silver, zinc-cadmium and zinc-aluminum are examples of eutectic forming systems. 2.8.1 Bismuth-cadmium system Condensed phase rule will be applicable to the alloy system as the gaseous phase is practically absent. Pure bismuth melts at 271° C and pure cadmium melts at 321° C. The two metals are completely miscible in the liquid phase. Addition of cadmium to pure liquid bismuth lowers the freezing point below 271° C and similarly addition of bismuth to liquid cadmium lowers the freezing point below 321° C. ‘The cooling curves for a few compositions (dark lines) and the phase diagram are shown in Figure 2.6. BGI CO) a7 e) ae temperature eo wt. % cadmium Fig. 2.6 Phase diagram of bismuth-cadmium system The line AE represents the freezing point curve of bismuth as cadmium is added to pure bismuth, The freezing point decreases continuously with added cadmium till the lowest freezing temperature (144° C) at £ is reached for 40% cadmium ~ 60% bismuth mixture, Further addition of cadmium results in its separation as solid phase, as it does not go into solution. Along the line AE the system is univariant with one degree of freedom (F = 3 - P= 3-2= 1). The line BE represents the freezing point curve of cadmium and the effect of the addition of bismuth to cadmium. The freezing point gradually decreases till it reaches the lowest temperature at . The line BE is also univariant just as the line AE. The two lines AE and BE meet at E which is the eutectic point where the three phases namely, solid bismuth, solid cadmium and their solution, coexist and the system is invariant with no degrees of freedom (F = 3 - P= 3 - 3 = 0), It represents a fixed temperature of 144° C (eutectic temperature) and a fixed composition of 40% Cd + 60% Bi (eutectic composition). No mixture of bismuth and cadmium has a melting point lower than this composition.38 Engineering Chemistry The eutectic mixture has certain characteristic features. The mixture with an eutectic composition shows a sharp melting point just like a compound. However the eutectic mixture is not a compound as the two components are not present in a molecular ratio. When one of the components is added to the eutectic mixture the mixture melts at a higher temperature ( in contrast such an addition to a compound will either decrease the melting point or does not alter it). The physical properties of the mixture (¢.2., density) are equal to the mean values of the two components. ‘The area above the curve AEB includes the liquid phase containing the completely miscible bismuth and cadmium, Cooling the liquid of composition x down the dotted line is possible till the temperature reaches the intersection point of the dotted line with the line AE. At this temperature solid bismuth crystallises out. Further cooling brings out further crystallisation of bismuth and the liquid becomes richer in cadmium and the freezing point of the liquid decreases till it reaches the eutectic temperature. Cooling the liquid of a composition y down the dotted line is feasible till the temperature reaches the intersecting point between the dotted line and line BE. At this point cadmium crystallises out and the remaining liquid becomes richer in bismuth with its freezing point moving down towards the eutectic temperature. 2.8.2 Lead-silver system The two component lead-silver system is similar to the bismuth-cadmium system in that, the metals are miscible in the liquid state, while in the solid state they form an eutectic mixture of a composition 2.6% Ag + 97.4% Pb melting at 303° C. The phase diagram (Figure 2.7) shows the freezing point curves AE for silver and BE for lead meeting at the eutectic point E. The descriptions of the lines, areas and the invariant eutectic point are similar to the description given for the bismuth-cadmium system. (961°C) 4 temperature eo 1B (327°C) solid Pb + liquid eutectic + solid Pb 0 20 80100 Fig. 2.7. Phase diagram of lead-siiver system ‘The phase diagram is useful in the recovery of pure metals from alloys of different compositions by fractional crystallisation. This is of practical significance in the Pattinson’s process of desilverization of lead. If the melt of a sample of argentiferous lead containing more than 2.6% of silver is allowed to cool from point x along the dotted line, pure silver will crystallise out along line 4’E till the remaining liquid reaches the eutectic composition containing 2.6% Ag. Similarly if the melt contains less than 2.6% Ag, pure lead will separate out, leaving the liquid richer in silver, along the line BE till the eutectic composition is reached.__ Phase Rule . 9 2.9 Systems Involving Compound Formation The two components 4 and B may interact to form a compound with a definite stoichiometric composition and a sharp melting point. If the composition of the compound remains the same in the solid and the liquid states the compound is said to have a congruent melting point. In some systems compounds are formed but the compounds are not stable till their melting point. When such compounds are heated instead of melting congruently they decompose to yield a new solid phase and a solution of composition different from that of the solid phases. The compound is said to undergo a transition called peritectic reaction ot incongruent fusion. 2.9.1 Compound formation with congruent melting The phase diagram of such a system shows two eutectic points separated by a hump as shown for a zine- magnesium alloy system (Figure 2.8). The composition corresponding to the hump is useful in deducing the formula of the compound and the maximum point of the hump indicates the melting point of the compound. The compound formed in the zine-magnesium system is MgZn, with a congruent melting temperature of 590° C € 650°C 590°C] MgZny+ soluti temperature co 420°C 4 zy 380° Cl Zn + solution sareC ‘Zn + MgZny MyZn,+ Mg 1 L L 1 o 2 40 60 30100 wt. % Mg Fig. 2.8 Phase diagram of @ Mg-Zn alloy system ‘The metals zine and magnesium melt at 419.5° C and 650° C respectively. The phase diagram may be considered as a combination of two phase diagrams of simple eutectic forming systems (e.g. Bi-Cd or Pb-Ag system) placed side by side. The part of the phase diagram on the left side consists of the two components Zn and MgZn, while that on the right consists of the two components MgZn, and Mg. The line AE, represents the boundary between the liquid and solid zinc and similarly the line CE, represents the equilibrium between the liquid and solid magnesium. The two eutectic points £, and £, have compositions of Zn (71%) + MgZn , (21%) melting at 380° C and MgZn, (61%) + Mg (39%) melting at 347° C respectively representing the invariant systems. The curve E, BE, encloses a region in which the liquid and solid MgZn, coexist. The maximum point B of the hump E BE, corresponds to a composition of MgZn, (Mg (33.33%) + Zn (66.7%) with a congruent melting point at 590° C. Thesharpness of the maximum is indicative of the stability of the compound while a flat maximum as shown in the present case is indicative of appreciable dissociation of the compound. 2.9.2. Compound formation with incongruent melting The phase diagram of the gold-antimony system forming a compound 4B, (AuSb,) with an incongruent ‘melting point is shown in Fig. 2.9. The point D represents the hypothetical melting point of the compound called peritectic point (Gk. = melting around). The compound on melting decomposes and yields pure Bas the new solid phase and a liquid whose composition is different from that the pure solid B or the solid compound 4B,. The solid in the region to the right of the dotted line DD’ consists of two phases, a core of B surrounded by a coating of AB,. The point E represents eutectic point. tem; eo) 4 A+ liquid wt % of B Fig. 2.9 Phase diagram of a system forming a compound with incongruent melting (e.9. Au-Sb system) 2.10 Partially Miscible Solids Examples of partially miscible solids include the lead-tin system and the copper-aluminum system. 2.10.1 Lead-tin system Lead is soluble in tin only up to 2.6% while tin is soluble in lead to the extent of 19.5% forming solid solutions. The phase diagram of the lead-tin system is shown in Figure 2.10. Lead melts at 327° C while tin melts at 232° C. The lead-rich solid solution is called a- phase and lies to the left-end of the diagram (to the left of the curve ADF. The phase is a saturated solution of tin in lead. The tin-rich phase called the phase lies at the right end of the diagram (to the right of the curve BCG) and is a saturated solution of lead in tin. A miscibility gap exists corresponding to the coexistence of a- and B- phases in equilibrium. Three phases a-, f- and the liquid can coexist and the system based on condensed phase rule becomes invariant. The phase diagram exhibits a discontinuity which may be either a eutectic point or a transition . Eutectic point is shown by the lead-tin system. The curves AE and BE are the liquidus curves while the ADE and BCE are the solidus curves. The points D and C represent the maximum solubility of tin in lead and lead in tin respectively. The solubility decreases with the decrease in temperature. AtPhase Rude 41 oe the eutectic point E the solid phases in equilibrium are the conjugate solid solutions and not the pure components. The curves DF and CG represent the variation of the composition of the conjugate solid solutions as a function of temperature. The eutectic mixture melts at 182° C and contains 60% lead. G2PC) 4 BPO) — (as liguid) (liquid +8) arp 8 wt. % of tin 108, Fig. 2.20 Phase diagram of lead-tin system Lead-tin alloys are fusible and are used as solders for metal-joining processes. The eutectic alloy of 60% lead-40% tin is used for soldering of electrical connections which require a metal-metal bonding with minimum heating. The more common plumber's solder has a composition of 50% lead- 50% tin melts rapidly, flows freely and with a wider range of freezing allows the wiping of the joint while the alloy is still in a pasty condition. It also provides a bright surface finish after soldering. Printing industry uses type metal, a ternary alloy of lead, antimony and tin. The addition of antimony to the lead-tin alloy hardens it and also makes the alloy expand on solidification. 2.10.2 Copper-aluminum system ‘The two metals are partially miscible in the solid state. The phase diagram is shown in Figure 2.11. B (626° C) C (590°C) Wt. % of copper 6 Fig. 2.11 Phase diagram of copper-aluminum systemThe solid solution « is formedat lower concentrations of copper in aluminum, thepoint D corresponding to 5.7% of copper. The point E at 548° C represents the eutectic between the solid solution c and another intermediate solid solution 8. The eutectic solid contains 5.7% of copper while the eutectic liquid has a composition of 33% copper. Copper-aluminum alloy containing 8% copper and the rest aluminum contains a mixture of @ phase and the eutectic @ + @ solid solution. The alloy finds extensive use as a casting alloy in aluminum foundries, The alloy also with small amounts of silicon, iron and zine has good mechanical properties and is used in automobile industry for crank cases, transmission housings, in washing machines and vacuum cleaners. 2.11 Interstitial Solid Solutions: Iron-Carbon System Interstitial solid solutions are formed when the alloying elements differ widely in and are best represented by the iron-carbon system. Pure iron is not useful for fabrication of structural components because of its weak mechanical properties. Carbon, though a non-metallic element forms alloys with iron to give various types of steel and improves the mechanical properties of the base metal to a large extent. The size of carbon atoms is small compared to that of iron atoms and hence occupies interstitial positions in the lattice formed by the iron atoms. The miscibility or solubility of carbon in iron depends on the crystal structure of iron, which in tum depends on the temperature, as pure iron exists in three allotropic modifications of a, 7 and 6 forms. The cooling curve of pure molten iron shows the allotropic transformations as shown in Figure 2.12. 1535°C temperature (° C) ‘1400° C 910°C 768°C The low temperature allotropic form called the a-iron has a body-centered cubic (BCC) structure which is stable up to 910° C. The metal is soft and ductile and shows ferromagnetic properties below the Curie temperature of 768° C. In the temperature range between 910° C and 1400° C, y-iron with a bigger face-centered cubic (FCC) structure is stable. This allotropic form is also soft and ductile. The high temperature allotropic form é-iron has a BCC structure and is stable beyond 1400? C till it melts at 1535° C. None of the allotropic forms of pure iron are as useful as their alloys with carbon.Phase Rule The solubility of carbon in BCC a-iron is quite low (~ 0.3% w/w) due to the small size of the interstitial sites which cannot accommodate even small atoms such as carbon. When the carbon content increases beyond 0.1%, a-iron changes over to 7- iron. The y- iron can dissolve carbon to an increased extent of 1.7% wiw, The interstitial solid solution of carbon in y- iron is called austenite steel. The transition temperatures of iron are influenced by the alloying elements, particularly carbon. For example the transition temperature of pure a-iron to » iron occurs at 910° C but with 0.3% carbon the transition commences even at 700° C and is completed at 800° C. With higher carbon content the whole transition is completed at around 700° C. Pig iron as obtained from the blast furnace contains more than 4.3% carbon. The carbon is burnt off to give wrought iron containing less than 0.02% carbon. Wrought iron is extremely tough and ductile. It can be easily welded and forged. Cast iron is also an alloy containing carbon > 1.7% (up to 6.67%) and the excess carbon existing as graphite or as iron carbide, Steel is manufactured in the open hearth or Bessemer process by burning away the excess carbon and bringing down its percentage below 1.7%. Iron alloys containing carbon in the per cent range of 0.03-1.7 are called mild steels. Steel is an inhomogeneous mixture of ferrite and cementite. The mass is known as pearlite because of its peculiar layer structure consisting of alternate layers of ferrite and cementite. Ferrite is a solid solution of carbon in a-iron with a maximum carbon content of 0.035% at 723° C and 0.007% at room temperature. Ferrite is often considered to be pure a-iron. Cementite is iron carbide with a specific composition of Fe,C (not molecular compound) and a complex orthorhombic structure. Asteel of purely pearlite structure (0.8% carbon) is too hard to be of any structural use. The structure of steel containing 0.2-0.3% carbon is about one-third cementite and two-thirds ferrite while with 0.6% carbon the steel is composed of two-thirds cementite and one-third ferrite. More of ferrite makes pearlite soft and more of cementite makes it hard. The desired qualities of steel such as softness or hardness and toughness or brittleness for specific uses depend on the fineness or coarseness of the structure of ferrite and cementite, The structure and the grain size are controlled by quenching and/or annealing at critical ranges of temperature and the operation is generally called heat treatment of steel. The formation of different phases in the iron-carbon system is conveniently explained with a phase diagram (temperature-composition diagram) shown in Figure 2.13 It can be seen that the composition is restricted to 6.67% of carbon and the phase diagram is actually that of ;-iron-iron carbide (F,C) system. The iron carbide decomposes at higher concentrations of carbon. When carbon is dissolved in pure molten iron, the freezing point (1535° C) decreases as d-iron is formed. As the carbon concentration increases beyond 0.5% the &phase disappears and the freezing point continues to decrease till 1130° C, the eutectic temperature at which the carbon content is 4.3%, The iron-carbon alloy containing 4.3% carbon solidifies instantaneously at the eutectic temperature into a mixture of austenite and cementite called Jedeburite. Ledeburite is the major phase of pig iron and contributes to the hard and brittle nature of pig iron. At temperatures lower than 723° C ledeburite transforms into pearlite and cementite. Molten alloys containing less than 4.3% carbon solidify gradually on cooling passing through a pasty consistency. Addition of carbon beyond 4.3% till 6.67% increases the freezing point along the curve EB and beyond the carbon content of 6.67% cementite decomposes. The transformation of pure y-iron (1400-910° C) with an increasing carbon content is shown in Figure 2.13. The curve DF represents the decrease in the freezing point of j-iron below 910° C as more carbon dissolves in the bigger FCC structure. The point F is the second eutectic point in the iron-carbon phase diagram at 723° C and carbon content of 0.83%, The eutectic occurs in a completely solid region and hence, it is called a eutectoid (eutectic like). Pure iron changes from the yto a form only at 910° C but this transition is shifted to a lower temperature of 723° C when iron is alloyed with 0.83% carbon. At this eutectoid temperature the austenite phase decomposes instantaneously into the pearlite phase.44 Engineering Chemistry a ——-+ ‘The formation of austenite or pearlite can be understood from the phase diagram. For example on cooling a sample of hypocutectoid steel containing less 0.8% carbon, along the line xx in the phase diagram, solid austenite separates at point a on the curve AE. The separation of austenite is completed at point 6 on the curve AC. Further cooling results in the separation of ferrite at point ¢ on the curve DF. ‘The composition of separated ferrite varies along the curve DG while that of the remaining austenite varies along DF. As the temperature decreases to the eutectoid temperature of 723° C precipitation of the eutectoid mixture (pearlilte) of ferrite and cementite from austenite occurs. 138°C 4 g B 2 . go Cemmentite + liquid ge g 1130" C c austenite + cementite D mC) : 4 ‘cementine + pearlite Ox y wi, % carbon 667% Fig. 2.13 Phase diagram of iron-carbon system Peartlite is the only phase obtained when steel with 0.8% carbon is cooled from higher temperatures to 723° C, Steel with carbon content greater than 0.8% (hypereutectoid steel) is cooled along yy, austenite separates out at the point d on the curve AE and the process is completed at point ¢ on the curve AC. Further cooling results in the separation of cementite at a point fon the curve FC. Once the temperature reaches 723° C pearlite formation occurs at the point g on the line FH. At lower temperatures a mixture of pearlite and cementite exist. Cast iron containing less than 4.3% carbon on cooling undergoes transformations along the line zz represented by points / along the curve AE, i along CE and j along FH. Austenite begins to separate at point h and at point / (1130° C) the eutectic mixture of ledeburite (austenite and cementite) separates out. The eutectic mixture on cooling transforms gradually into cementite with the composition varying along CF till the point / where the remaining austentite changes into pearlite, The phases formed in the iron-carbon system under equilibrium conditions only are shown in the phase diagram, Equilibrium conditions are established only when the cooling rates are very slow. When steel is quenched, that is cooled rapidly, austenite undergoes diffusionless transformation to a metastable phase called martensite (named after the German metallurgist Martens), Martensite is a supersaturated interstitial solid solution of carbon in a-ferrite with a distorted BCC or tetragonal structure. MicroscopicPhase Rule 45 examination of martensite reveals a series of fine needle like structures. Martensite is extremely hard and strong, the hardness being attributed to the efficient filling up of the void space in the BCC structure with carbon atoms which prevent slippage between planes of iron atoms. Another metastable phase called bainite (named after the American metallurgist Bain) is formed when steel is quenched to temperatures between 535° C and 260° C and allowed to undergo isothermal transformation. Bainite consists of a mixture of ferrite and cementite with fine needle like structures. 2.11.1 Heat treatment of steel Heat treatment involves the combination of heating and cooling of a metal or alloy in one or more temperature cycles to confer desirable physical properties to the metal or alloy. Heat treatment of steel may be carried out under near equilibrium conditions to improve the duetility or under non-equilibrium conditions to enhance the hardness. During heat treatment the size and shape of the grains or the composition of the phase undergoes changes with respect to the microconstituents. In addition any internal stresses present are relived. Plain carbon steel on heating to a temperature > 723° C and maintained at this temperature for a sufficiently long time allows the formation of the austenite phase and the dissolution of more carbon in the FCC structure. On slow cooling of the austenite phase transformation of FCC to BCC occurs and the excess carbon forms cementite. If the steel is quenched by plunging into water or oil to 204° C or a lower temperature the carbon atoms do not have sufficient time to form cementite but remain trapped in the BCC lattice, The excess carbon precipitates out in the hot metal and prevents the slipping of the planes. Thus quenched steel is quite hard and strong but has lower ductility. This heat treatment is called transformation hardening. Hardening involves the transformation of austenite to martensite or the bainite phase, making the steel hard. The quenched steed is not useful for construction purposes because of its brittleness. Therefore quenching is always followed by another heat treatment process called tempering, ‘The quenched steel is tempered by reheating to below the a-iron- to-y- iron transition temperature. The residual stresses and strains are relieved and the excess of carbon is rejected in the form of e-carbide (Fe, ,C). By tempering the steel becomes tougher and ductile. Tempering is carried out at about 200° C to make hard steel resistant to abrasion or at higher temperature (~540° C) to make tough steel capable of withstanding shock loads. Annealing involves heating and holding the stee! at a suitable temperature for some time to facilitate the dissolution of carbon in y- iron followed by a slow cooling in a controlled manner in a furnace. Steel is softened and becomes ductile and machineable. However annealing decreases the hardness and strength of steel. Annealed hypereutectoid steels contain cementite. They are not soft but can be machined easily. In contrast annealed hypoeutectoid steels contain ferrite and are relatively soft and malleable. Normalizing is yet another heat treatment involving the cooling of the hot steel more rapidly as compared to annealing but less rapidly when compared to quenching, usually carried out to convert a soft and ductile steel into a strong and ductile sample. The homogeneous structure of steel is recovered with refinement of grains and removal of internal stresses. Toughness increases and the normalized steel is amenable for use in engineering works. Case hardening is a surface treatment by which the inside soft core of steel is hardened on the surface. Low carbon steels are case hardened because they cannot be hardened by quenching. The two step process involves carburizing followed by hardening. Carburizing involves heating the mild steel article surrounded by pieces of charcoal in a cast iron box to about 900° C for a sufficient length of time (about °-4 hours) to allow for the adsorption of carbon on the surface of the article to the required depth of46 Engineering Chemistry -~——+ about 0.08-1.5 mm. The outer skin of the article is converted to a high carbon steel containing 0.8-1.2% of carbon. Gas carburizing is a method of heating the mild steel article in the presence of gases rich in hydrocarbons (¢.g.,coal gas) to surface harden the material. The carburized steel is then hardened in the second step by heating to 900° C and quenching in oil followed by re-heating to about 700° C and quenched in water. The outer surface of the article is hardened by this treatment. Nitriding produces a hard surface on alloy steels. The process involves heating the alloy in the presence of ammonia to about 550° C. Ammonia decomposes and the nitrogen formed combines with alloying elements to form hard nitrides on the surface of the alloy. Cyaniding also produces case hardened medium carbon steel articles. The article is immersed in a molten bath of sodium or potassium cyanide at about 850° C for some time to facilitate the adsorption of both carbon and nitregen and then quenched in oil or water. Solved Examples. 1. Apply phase rule to calculate the (a) the degrees of freedom at triple point and for the phase equilibrium S_= Sy; (b) the number of phases in the equilibrium MgCO,(s) = MgO(s) + CO,(g) and (c) for the thermal decomposition of NH,Cl (s) = NH(g) + HCI (g); and the number of components in H,0() = Hyg) + 40g) and Ag(s) in equilibrium with Pb + Ag liquid. Solution: (a) Fat triple point'= C-P+2=1-3+2=0 (Since: land P=3) F forthe S,=S, equilibrium 1-2+2=1 (Since C= 1 and P= 2) (b) No. of phases in MgCO, (s) = MgO (s) + CO,(g) =3 (two solid phases + 1 gas phase) No, of phases in NH,Cl (s) = NH; (g) + HCl (g); =2 (1 solid +1 gas phase) (©) No. of components in H,0(I) = H, (g) +%0, (g) st No. of components in Ag(s) = Pb + Ag liquid = 2 : 2. A.10 kg of alloy of bismuth and cadmium contains 23% Cd. Calculate the mass of Bi in the eutectic if the ‘eutectic composition contains 40% Cd and the mass of the eutectic solid. Solution: Cd content in 10 kg =2.3 kg, ‘and the Bi content =7.7 kg. If the eutectic composition contains 40% Cd corresponding to 2.3 kg of Cd the mass of Bi in the ‘eutectic = (2.3 * 60)/40 = 3.45 kg of Bi. Mass of eutectic solid =2.3 + 3.45 = $.75 kg, . 3. A 100 kg molten alloy of lead-silver containing 0.15% of silver was cooled to form an eutectic with 2.6% silver. Calculate (a) amount of silver that can be recovered from the eutectic mass and (b) the mass of lead that separates out. Solution: Mass of silver in 100 kg of alloy in 0.15 kg. Mass of silver in eutectic = (0.15/2.6) « 100 = 5.769 kg Mass of lead that separates out = 100 ~ 5.769 = 94.231 kg. Review Questions SSS 1. State the phase rule and explain the terms involved with suitable examples. 2. Discuss the application of phase rule for ice-water-water vapour system. 3. How are the different phases of the one-component sulphur system represented in the phase diagram? Give an account on the various transitions with the help of the phase diagram. 4. What is condensed phase rule?Phase Rule a7 ‘Write « note on thermal analysis. How are the heating and cooling curves useful? Discuss the temperature-composition diagram of completely soluble metals. What is eutectic point? Discuss the characteristics of the eutectic point with specific reference to the bismuth- ‘cadmium system. Discuss the phase diagram of lead-silver system and its use in obtaining pure metals. Explain the terms congruent and incongruent melting of alloys. Discuss the phase diagram of the magnesium-zine system. What are solders? What is their use? How can you explain the formation of solders with the help of phase diagram, Write a note on copper-aluminum casting alloys. Discuss in detail the phase transformations in pure iron. ‘What are interstitial solid solutions? Discuss in detail the iron-carbon phase diagram and its relevance to the heat treatment of steel Explain the terms case hardening, normalizing, nitriding and cyaniding.SOLID STATE 3.1 Introduction Matter consists of an aggregate of molecules existing in three different states—solid, liquid and gas. Gases and I iquids have no definite or permanent shape and take the shape of the container in which they are placed. A gas occupies the entire volume of the container while a liquid exhibits a surface limiting its volume. Both gases and liquids are sensitive to variations of temperature and pressure. Solids are the most complex form of a molecular aggregate, with a definite three~dimensional shape. Solids are relatively more dense, hard and strong in retaining their shape. The shapes of solids are relatively stable and are not affected nuch by changes in temperature or pressure. Solids exhibita wide variety of physical and mechanical properties such as electrical and thermal conductivity, hardness, strength, toughness, etc. It is these characteristic features of solids that renders them useful for engineering applications of fabrication and construction under * variety of situations. 3.2 Amorphous and Crystalline Solids Solid substances exist in two types (i) amorphous solids (ii) crystalline solids. Amorphous solids resemble liquids in that, they do not have an ordered structure, i.c., an orderly arrangement of atoms or ions in a three-dimensional structure. These solids do not have a sharp melting point and the solid to liquid transformation occurs over a range of temperature. The physical properties exhibited by amorphous solids are generally isotropic as the properties do not depend on the direction of measurement and show the same magnitude in different directions or Cartesian axes. Glass is a good example of an amorphous solid which is quite rigid and incompressible. X-Ray diffraction studies on glass show concentric rings indicating that solid glass has a certain amount of order but not a completely ordered structure. The absence of the long-range order is also indicated by the breaking pattem of glass. Glass breaks into conchoidal shapes instead of cleaving into flat surfaces or faces with characteristic angles between faces. Other examples of amorphous solids include solid polymers and plastics. Crystalline solids in general are characterised by their rigid and incompressible nature with sharp and high melting points. Many of the crystalline solids exhibit an anisotropic behaviour in their physical, optical, mechanical and electrical properties. Crystalline solids have a highly ordered arrangement of constituent atoms, ions or molecules in a three-dimensional layer or lattice, giving rise to distinct geometrical shapes. The external shape of a crystalline solid is called its habit. The habit varies depending on the conditions during the growth of the crystal. Thus sodium chloride crystallises in the form of cubes from an aqueous solution, but its habit can be modified into octahedral shape by the addition of a habit modifier such as urea. Addition of a trace of potassium ferrocyanide to brine modifies sodium chloride crystals into needles or dendrite type. Similarly raffinose naturally present in sugar beet modifies sucrose crystals to a cubic appearance at a concentration of about 1%, but at higher concentrations (~2%) it modifies sucrose crystals into thin plates.Solid State - 49 3.3 Crystallography Crystallography is the branch of science involving the study of the shape or geometry of crystals, their properties and internal structures. Optical or geometrical crystallography and X-Ray crystallography are the two major methods of study in vogue at present, the first method is used on the external morphology and the second method on the internal structure. 3.4 Optical Crystallography Optical or geometrical crystallography involves the study of the extemal geometry of crystals by visual examination developed by geologists and mineralogists. All crystals show flat surfaces called faces, sharp edges formed by the meeting of two faces and vervex or corner at the intersection of three or more edges. The overall geometry or shape of the crystal can be described in terms of polyhedra arising out of a combination of faces, edges and vertices as given by the Descartes-Euler theorem, which states, that face + vertices = edges + 2. The application of the theorem to different polyhedra commonly found in erystals is shown in Table 3.1. ‘Table 3.4 Different polyhedra seen in crystals Polyhedron Faces | Vertices | Edges | No. of faces meeting at the vertex - ‘Tetrahedron | 4 4 6 3 triangles Octahedron 8 6 2 4 triangles Cube 6 8 2 3 squares Icosahedron 20 2 30 5 triangles Dodecahedron | __12 20 30 3 pentagons 3.5 Laws of Crystal Structures Geometrical crystallography resulted in the enunciation of laws of crystal structures in the form of: (i) constancy of interfacial angles: (ji) rationality of indices and (iii) symmetry. 3.5.1 The law of constancy of interfacial angles The law states that, the corresponding faces or planes forming the external surface of a crystal of a given substance always intersect at a definite angle which remains constant at a given temperature no ‘matter how the face develops. Thus, for example, all the interfacial angles of cubic sodium chloride crystals are found to be 90° independent of the size and shape of faces. 3.5.2 The law of rationality of indices ‘The law put forward by Abbe Haily states that, the ratio between intercepts on crystallographic axes for the different faces of a crystal can be expressed by rational numbers. The law can be explained with the help of a plane ABC with intercepts along O4, OB and OC along the x, y and z axes at distances of 2a, 3b and 3c respectively as shown in Figure 3.1. The coefficients a, 6 and c are known as Weiss indices of'a plane.