MATERIALS THERMODYNAMICS With Emphasis on Chemical Approach HAE-GEON LEE A iene esetvaca eT [bb MATERIALS THERMODYNAMICS With Emphasis on Chemical Approach A PREST. PeOM. Mot. Whtbo JALIERIANA —MeT- A RR SR a HAE-GEON LEE POSTECH, Korea MAA 2013 UNIVERSIDAD TECNICA FEDERICO SANTA MARIA BIBLIOTECA CENTRAL INVENTARIO: I 3@0 3 Pains AmAzons sf 100, 82 Scientific ANGHAI « HONG KONG + TAIPEI CHENNAPreface This book is the expanded edition of the first book entitled “Chemical Thermodynamics for Metals and Materials.” This book presents thermodynamics of materials with emphasis on the chemical approach. This expanded edition keeps most of the contents of the first edition, but with substantial revisions. It also includes a number of additional topics of thermodynamics, Which are relevant to the wide spectrum of materials. This book is thus suitable to students in materials science and metallurgical engineering, and also to students in related fields such as physical chemistry and chemical engineering. ‘As thermodynamics is @ key discipline in most science and engineering fields, a great number of books, each of which claims originality and uniqueness in presentation and approach, have been published on the subject. However, thermodynamics remains a subject that is difficult to grasp for many uninitiated students and an “easy to forget” one for graduate engineers. After many years of teaching thermodynamics at different universities and conducting actual application of ita the industry level, Ihave come to the following conclusions * each of the thermodynamic topics must be explained so as to make a cleat connection to its physical significances, and Fa ‘© mathematical derivation of thermodynamic relationships must be easy to follow in its sequential flow. This book has been written with such insights as guiding principles. As such, it has unique features as described below: ‘Classical thermodynamics is amalgamated with statistical approach, wherever it provides a better understanding. While this book is essentially based on classical thermodynamics, it is supported by statistical treatments with molecular-level models, wherever it helps to make understanding of a particular concept easier. ‘This combination should help readers obtain a solid grasp of physical significance, which may otherwise remain as concepts that are difficult to comprehendviii Materials Thermodynamics with Emphasis on Chemical Approach ‘+ In contrast with most books on this subjects in which mathematical derivation of thermodynamic relationships is explained line-by-line in @ largely one-dimensional ‘ay, this book adopts a two-dimensional approach in which the derivation flows in ‘wo ways: vertically and horizontally. This flowchart-like format should provide readers with clear reasoning of the derivation flow. A mumber of worked examples are included in each chapter, which are designed to emphasize extended principles and to present the strategies of applications. Many exercise questions which helps develop skills necessary to handle numerical problems are also included in each chapter. ‘A computer-aided learning package is included with this book in an accompanying CD- ROM, which simulates the way a lecturer would teach this subject in classroom setting Unlike the typical non-interactive presentation found in most textbooks, this multimedia package provides the users with helpful interactive learning tools. The package includes ‘much of the contents contained in the book as well as the solutions to the exercise questions, As this book has developed from my teaching materials, it unavoidably includes Contributions of many other authors. 1 wholeheartedly acknowledge their contributions. 1 am indebted to my teacher, Professor Y.K. Rao for introducing me to the world of | thermodynamics. Iam especially grateful to my former colleague, Professor Peter Hayes, at The University of Queensland, Australia, for making many useful comments and giving me constant encouragement. | am also thankful for the assistance provided by my colleague, Professor Youn-Bae Kang in proof-reading parts of the book, and providing constructive comments. | dedicate this small achievement to the late chairman Chang Sang-Tae of Dongkuk Steel Co., who offered me unconditional support and encouragement for my academic career. He was indeed my mentor for my whole life, having taught me the ways to harmonize knowledge with wisdom, 1 wish to acknowledge generous support of POSCO, which has enabled me to apply thermodynamics to the industry level. Finally, 1am deeply thankful to my wife and children for the love, support and encouragement they have given to me. Hae-Geon Lee POSTECH Pohang | : | eeContents Preface a s. Introduction 14 Energy 2 12 Heat and Work 4 ‘The First Law of Thermodynamics 2.1 The First Law of Thermodynamics 7 2 Enthalpy and heat Capacity 15 23 Enthalpy Change 23 ‘The Second Law of Thermodynamics 3.1 Grades of Energy 27 3.2 Heat Engines and Entropy 32 33. Energy Dispersion and Entropy $3 34 Equilibrium Criterion and Entropy 62 35. Entropy Changes and Entropy Productions 73 3.6 Statements ofthe Second Law of Thermodynamics 94 Free Energy Functions 4.1 Energy Functions 97 42. Helmholtz Energy 99 43 Gibbs Energy 101 44 Effect of Pressure on Gibbs Energy Change 108 45 Effect of Temperature on Gibbs Energy Change 106 46 Some Useful Equations 107 ‘The Third Law of Thermodynamics 5.1 Statements ofthe Third Law 111 52. Corollaries tothe Third Law 112 53. Absolute Entropies 115 27 7 ax Moterials Thermodhnamics with Emphasis on Chemical Approach 5.4 Molecular Interpretation 116 6. Enthalpy and Gibbs Energy Changes 119 6.1 Standard States 119 6.2 Heat of Formation 120 63 Heatof Reaction 122 64 Adiabatic Flame Temperature 127 65. Gibbs Energy Changes 129 Behavior of Gases 133 7.1 Weal Gases 133 7.2 Real Gases and Fugacity 136 8. Thermodynamic Functions of Mixing 141 8.1 Activity 141 82 Partial Properties 148 Behavior of Solutions 157 9.1 Ideal Solutions 157 92 Non-ideal Solutions and Excess Properties 161 93° Dilute Solutions 167 94 Gibbs-Duhem Equation 171 95° Solution Models 175 10. Reaction Equilibria 185 10.1 Equilibrium Constants 185 10.2 Criteria of Reaction Equilibrium — 190 10.3 Effect of Temperature on Equilibrium Constant 201 10.4 Effect of Pressure on Equilibrium Constant 203, 10.5 Le Chatelier's Principle 205 10.6 Alternative Standard States 207 10.7 Interaction Coefficients 215 10.8 Ellingham Diagram 218 10.9 Adsorption Equilibria 227 11. Phase Equilibria 239 111 Phase rule 239 11.2 Phase Transformations 248 11.3 Phase Equilibria and Gibbs Energies 255 114 Influence of Interfaces on Equilibrium 271 12. Phase Diagrams 287 12.1 One Component (Unary) Systems 287 12.2 Binary Systems 297 123 Thermodynamic Models 326Bk ra Conens x 12.4 Temary Systems 335 12.5 Predominance Diagrams 363, 13. Electrochemistry 367 13.1 Basic Electrochemical Concepts 367 132 Electrochemical Cell Thermodynamics 370 133 Electrochemical Cells and Electrodes 378 13.4 Concentration Cells 390 135 Activities in Aqueous Solutions 403 13.6 Solubility Products 411 13.7 Pourbaix Diagrams 416 Appendices 427 Appendix 1 Heats of formation, standard entropies and heat capacities 429 Appendix II Standard Gibbs energies of formation 436 Appendix II Properties of selected elements 449 Appendix IV Standard half-cell potentials in aqueous solutions 452 Index 455Chapter 1 Introduction ‘Thermodynamics is @ science concerned with the transfer and conversion of energy associated with various chemical and physical processes. It is temperature that plays the ‘central role in thermodynamics. Temperature is a fundamental notion since it is not expressible in terms of basic quantities like mass, length and time. This makes thermodynamies unique and different from other branches of science. The processes ‘which are subject to thermodynamic considerations include all of the phenomena that ‘occur in nature, and also include the chemical and physical processes that are ‘manipulated intentionally ‘Thermodynamics is limited only by completely general restrictions on macroscopic energy transfer in nature and hence exceedingly general in its applicability. It deals with the bulk (macroscopic) properties of matter and does not concern itself with whether or not there are atoms or molecules. In fact, thermodynamics does not care whether or not there are atoms and molecules. In this regard, it is sometimes called “classical thermodynamics.” On the other hand, statistical the rmodynamics which is footed on uantum mechanics deals with the individual particles of matter, and provides means for calculating the properties of bulk material (macroscopic samples) from the properties of the atoms and molecules which comprise the material require knowledge of the behavior of individual particles is called classical thermodynamics. Example: The pressure of a gas in a container is the result of momentum transfer of the particles (atoms or ‘molecules) to the wall of the container, but the behavior of individual particles does not need to be known in classical thermodynamics. A pressure gage is sufficient to measure the pressure. Classical Thermodynamics ‘Statistical Thermodynamics ‘The macroscopic approach to the study || The microscopic approach based on the of thermodynamics which does not average behavior of large groups of individual particles is called statistical thermodynamics. It provides a framework for relating the microscopic properties of individual atoms and ‘molecules tothe macroscopic or bulk properties of materials that can be observed. This ability to make macroscopic predictions based on microscopic properties isthe main advantage of statistical thermodynamicsMaterials Thermodynamics with Emphasis on Chemical Approach (Chemical thermodynamics in particular is the study of the interrelation of heat and work with chemical reactions or with physical changes of state. For example, it deals with determination of feasibility of transformation from one phase to another. It also establishes a criterion as to whether or not a particular chemical process can take place under any given conditions. How much of energy is required for the process and how far the process will go (the maximum yield) can also be determined, ‘The laws of thermodynamics are the results of concise summaries of experimental observations. Prerequisite to the understanding of the laws of thermodynamics is a clear Understanding of some basic terms like heat, work and energy 1.1 Energy Energy can be viewed as the ability to cause changes. Energy is an attribute of a substance as a consequence of its structure (atomic, molecular or aggregate). Matter is ‘made up of atoms and molecules (groupings of atoms) and the properties of the matter depend on the behavior of these particles. Energy causes the atoms and molecules to always be in motion, ‘Since a chemical transformation involves a change in the structure, it invariably causes the increase or decrease of energy of the substances involved, Energy can also be defined as the ability to do work. While there are many forms of energy, they can be grouped into ‘wo categories: potential energy, of stored energy; and kinetic energy, or energy of ‘motion. All of these energies are quantized: ie, it is not allowed to take any arbitrary value of energy, but only certain discrete numerical values of energy can be taken, Potential Energy The potential energy is the energy that atoms and molecules possess in the form of bonds associated with the intermolecular attractive forces. A form of potential energy which is of prime importance in chemical thermodynamics is chemical energy which is related to chemical bonds for the structural arrangement of atoms or molecules. Chemical reactions ‘occur by breaking the bonds and the corresponding chemical energy is released ot absorbed. When released (exothermic), it is either reused in forming new bonds with ‘other atoms or energizes atoms or molecules, or enters the surroundings as heat, Kinetic Energy All atoms or molecules at temperatures above absolute zero Kevin are in a state of ‘motion and hence possess the kinetic energy associated with their various motions. What kinds of motions are possible? The motions of individual atoms or molecules are random and chaotic, The motions are classified into three different modes; namely, translation, rotation and vibration. The kinetic energy is the sum of the energy due to these three ‘motions. The sum total of all of this microscopic-scale randomized kinetic energy withinInrodtion @ body is sometimes given a special name, thermal energy. Translation is the movement from fone location to another. Monatomic. molecules store the kinetic energy through the translational ‘motion, as itis the virally only possible motion for them. For solids and liquids, translational ‘motions of molecules are restricted to very short @” Translational mode @) rasa distances. But solids and undergo internal vibration and rotation. Internal energy Internal energy, U, is the sum of the kinetic and potential energies of all the particles (atoms or molecules) making up a body, and hence it involves energy on the microscopic scale. Atoms and molecules play the role of storage and transport of ‘energy, and conversion of energy from fone form to another by uptake or release of heat. The intemal energy does not include the kinetic and potential energies Of the system as a whole. For instance, the kinetic energy related to the motion of a massive body such as a baseball or a car that is moving along a uniform trajectory is not included in the internal liquids, and gas ‘molecules consisting of two or more atoms can a Vibrational mode Temperature ‘Temperature is a measure of the average kinetic energy of particles in a substance, which is related to how hot or cold that substance is. Temperature is not directly Proportional to the internal energy since temperature measures only the kinetic energy, but do not tell anything directly about the potential energy of the substance. Two objects with the same temperature do not in general have the ‘same internal energy. ‘energy of the body. It excludes any potential energy that a body may have because of its location in external gravitational or electrostatic field ‘The following diagram shows a schematic expression of the internal energy of two different materials at the same temperature. It is noted that at the same temperature, the average kinetic energy of the molecules is the same, but not the potential energy. Material A Kinetic Energy Potential Energy At the same temperature, the average kinetic energy of the molecules is the same, but not the potential energy. Material B Ta j Internal Energy4 Materials Thermodynamics with Emphasis on Chemical Approach ‘When energy is transferred into a substance, it can be used to increase the kinetic energy of particles (atoms or molecules), which causes increase in temperature. The energy can also be used to increase the potential energy of the particles, which does not cause increase in temperature. Internal energy is a property of a system that depends only on the current state of the system, not on how the state is reached. In thermodynamics this kind of property is referred to as a state function. Example 1.1 The internal energy (U) of a monatomic ideal gas is given as j=LNm Where 1 is the number of atoms and m is the atomic mass. According to the kinetic theory of gases, the mean-square speed of the atoms, , is given as, | 3PV / Nm | 1). Find out how U depends on temperature. 2) Determine how U depends on pressure or volume at a constant temperature. 1). By removing <*> from the two equations above, and knowing PY = nk, ‘Thus, U's directly proportional to 7. 2) From the above equation, Uis independent ofboth P and V at constant 7. 1.2 Heat and Work Heat and work are the only two mechanisms by which energy can be transferred to or from a body. It is important to understand clearly the difference between work and heat Work ‘Work is a form of energy transfer to or from the body that is due to a change of the external macroscopic parameters of the body (for example, expansion of the volume of a system against an external pressure, and driving of a piston-head out of a cylinder against ‘an extemal force.) By work energy is transferred due to organized motion of particles (ie., atoms, molecules, electrons, etc.). For instance, when a piston-head is driven to do work, all the atoms in the piston-head moved together in the same direction,Introduction 5 Heat Heat is the transfer of thermal energy. The energy transfer by heat occurs from a body at ‘a higher temperature to one at a lower temperature. In molecular terms heat is the transfer of energy via microscopic thermal (chaotic, random, disorganized) motion of atoms and ‘molecules When energy is added to a system in the form of heat, itis stored as kinetic and potential energy of the atoms and molecules making up the system, Heat transfer into the system and work done on the system can inerease thermal energy of the system. There is no way to detect any qualitative difference in the thermal energy resulting from any of these sources. For example, work in the form of violent agitation can increase thermal energy Units of energy 1 joule () =1 kg m’s® gem’s?=107) 1843 101.3253 of a system, but itis indistinguishable from that produced | j ywrj = 3.6 x 10° by direct heat transfer into it from some source at a higher oz x10) temperature, Neither heat nor work is thermodynamic property of a system. A system cannot contain ‘or store either heat or work. They are two different forms of energy transfer. ‘The sign convention is that, ‘+ Heat (q) is positive when it flows to the system from the surroundings and negative ‘when it flows from the system to the surroundings. ‘+ Work (1) is positive when the surroundings does work on the system, and negative when the system does work on the surroundings. Heat (g) ‘System: a portion of the universe that is chosen for thermodynamic discussion Surroundings | Surroundings: the remainder of the Work (w) universe. Caution: Some texts adopt different sign convention: Le., wis positive when work is done by the systemChapter 2 The First Law of Thermodynamics 2.1 The First Law of Thermodynamics The First Law of Thermodynamics is really a statement of the principle of conservation of energy: + Energy can neither be created, nor destroyed. ‘+ Energy can be transported or converted from one form to another, but cannot be either created or destroyed, * Chemical and/or physical changes are accompanied by changes in energy Energy may be converted from one form to another, but it cannot be created or destroyed. This principle is referred to as the First Law of Thermodynamics. The internal energy of the system (U) increases, if heat (q) is supplied to the system, or work (1) is done on the system. The internal energy of the system (U) decreases if heat is extracted from the system, or the system does work (1) to the surroundings. Net change in the internal energy (AU) is then AU =q+w Example 2.1 Work can be expressed in terms of a force and the displacement of its point of action. If the gas inside the cylinder shown expands and pushes the piston against the external pressure Pj, can the force (F) exerted by the gas on the piston be represented by the following equation? F = AP,, where A is the cross sectional area of the piston8 Materials Thermodynamics with Emphasis on Chemical Approach As force = area x pressure, the expression is correct. If the gas expands against the external pressure P,, from L; to L; in the figure, the work done by the system (i.e, the gas) is 1 ", Pe we-[4p,dt=-[B,av 7 fi i If the external pressure is continuously adjusted so that it is La kept the same as the internal pressure P, L P wa-[ear ‘Work under these conditions is called reversible work nn es ll es Sete ie tg Ten | fitted with a frictionless piston which maintains the oxygen pressure at 1 atm. The | | iron in the steel fiber reacts with oxygen very slowly to form FeO;. Heat generated | by the reaction is removed during the process so a to Keep the temperature constant | at25°C. For the reaction of 2 moles of ion, 831.08 kJ of heat i removed aFe+30, = Fe,05 : Calculate heat (q), work (w) and internal energy change (AU). Assumptions: (2) The volume of oxygen = the total volume of the cylinder (Fe and Fe,Os are both solid and occupy a negligible volume compared with the gaseous O2,) (2) Oxygen is an ideal gas. PV =nkT T AV; volume change due to reaction ‘An: number of moles of O; reactedThe First Law of Thermodynamics ° | = Given: An = -1.5 moles and T = 298 K, Knowing R = 8.314 mol'K" =3.72K) w20 —work is done on the cylinder (system) AU=q +0 : First law ae 08 KI (given) [au =-s27360 | ea AU <0 — Decrease in bond energy (chemical energy) caused by chemical reaction Bonds of reactants (Fe and O;) break and new bonds of the products (FesOs) form. As the molecular bond energy of the products is smaller than that of the reactants, the balance of the bond energy is released as heat, and the internal energy decreases. Example 2.3 P A system can change from one state 10 + pas my another in many different ways. Suppose a > system changes from the initial state (A) in the figure to the final state (B), Determine the work done by the system for each of the following paths: Path |: A4C9B 5 ie Path? :A4EB q Final Path3 : A9D9B Recall that - ff Pav Path J: Initially the pressure decreased from P, to P:(ie., A-¥C) at the constant volume V; by decreasing the temperature. In this process no work has been done as there was no volume change. Next, the volume of the system expands from V to V3 (ie.,C—»B) at the constant pressure Ps. The amount of work done in this process is represented by the area CBNM. This is the total work done if the system follows the path 1 Path 2: Ifthe system follows the path A->E-+B, work done by the system is represented by the area AEBNM, Path 3: Similarly, the amount of work done by the system is given by the area ADNM. ‘The amount of work done by the system depends on the path taken, and hence cannot be evaluated without a knowledge of the path.0 Materials Thermodynamics with Emphasis on Chemical Approach | The g0s inside the cylinder shown expands and pushes the piston against | the extemal pressure Pa, Determine the work done by the cylinder for each Of the following paths: (1) Pe, suddenly drops to Py (2) Pe, drops to P; and then to Py (3) Po, drops in sequence to P,, P2, Ps and P, (4) Po, decreases in such a manner that it always infinitesimally | smaller than the pressure inside iy 7 the cylinder. y : ‘The shaded area in each case is the amount of work done by the cylinder (system) to the surroundings by volume expansion. () Pa Py ©) Pa PsP, | | Pt P. P| vi Vr Infntesimatly (A) Pe + Pi + Py + Py +P, 3) P. soni epee ea eas pf g infinite number” of stepsThe First Law of Thermodynamics u It is noted that, as the number of steps increases, the amount of work done by the system also increases for the same initial and final states. When the external pressure decreases by infinitesimally small steps, the work done by the system becomes maximum (the case 4). This represents the reversible process. All others are irreversible processes. Example 2.5 ‘The gas inside the cylinder shown below | is compressed by pushing the piston against the internal pressure P Determine the work done on the cylinder foreach of the following paths: (1) Pa is suddenly increased to Py (2) Pais increased to P; and then to P, G) Pais increased in sequence to P,, 2, Pyand Py (4) Pecis increased in such a manner that it always infinitesimally larger than the pressure inside the cylinder. () PoP; P| P| D P| P| vi vi ve vi Ininigsimaly | @ Paar PPP, 4) Pa [yr RABThe First Law of Thermodynamics B Example 2.6 ‘A substance in state A undergoes a change to state B 1 via state 1, and then comes back to state A via states 2 B and 3. Is it possible that the gain of internal energy in the forward process (A—+1-9B) can be different from ae the loss in the backward process (B->23A)? No. It should be the same. If different, the system will return to the initial state A with a net gain of internal energy. In other words, if different, the system will gain even more energy from nowhere just by repeating the process. This is contrary to the First Law of ‘Thermodynamics. Therefore the internal energy gained in the forward process must be ‘equal to the energy lost in the return process. We have seen here that internal energy (U) differs from heat (q) and work (v) in that it depends only on the state of the system, not on the path it takes. A function which depends only on the initial and final states and not on path is called state function. Path 1 U: State Function AU=U;-U, 91 442 #95. Wy pws, but, gu + wy = 92 + w Therefore, AU = + w ty SAU Patho Example 2.7 ‘Which of the following thermodynamic terms are state functions? ‘Temperature (7), Pressure (P), Heat (g), Work (w), Volume (1) ‘State functions: 7, P, V Non-state functions: g, w State functions depend on the mass of material which are called extensive properties (e.g., U, V). On the other hand some state functions are independent of the amount of ‘materials. These are called intensive properties (e,¢.. PT). * Thermodynamics is largely concerned with the relations between state functions which characterize systems. * A state function can be integrated between the initial (A) and final (B) states, being independent of integration path1“ Materials Thermodynamics with Emphasis on Chemical Approach (example) av = [Pav ‘+ An exact differential can be written in terms of partial derivatives. For instance, as U = ITN), + The order of differentiation ofa state function i immaterial. (3%) (28) war), |, arar ly * The First Law of Thermodynamics may be summarized bythe following equation: AU=q+w For infinitesimal change of state aU = dg + dw | But dg and ctw are not exact differential because they depend on the path. To remind us ofthis, they are customarily written as 8g and bw. aU = q+5w Exercises 2.1 Calculate the work done by one mole of an ideal gas when it isothermally expands from I m’ to 10 m’ at 300 K. 2.2. A system moves from state A to state B as shown in the figure. When the system takes path 1, 500J of heat flow into the system and 200J of work done by the system. (1) Calculate the change of the internal energy (2) Ifthe system takes path 2,100 J of work is path 4 done by the system. How much heat flows ® into the system? (3) Now the system returns from state B to state A via path 3.100 J of work is done on (@) Path 2 the system. Calculate the heat flow.The First Law of Thermodnamics Is 2.2 Enthalpy and Heat Capacity Enthalpy Ifa process takes place at constant volume, U=qew At constant volume, w= PAV =0 Therefore, the increase or decrease in internal energy of the system is equal to the heat absorbed or released, respectively, at constant volume. Ifa process is carried out at a constant pressure rather than at a constant volume, then the work done by the system as a result of the volume change is, fi pai From the first law of thermodynamics, AU =9+w AU =U; -U, | w=-PV,-%) (Uz + PV2)-(U + PK )=9 ‘The function U + PV occurs frequently in chemical thermodynamics and hence itis given ‘a special name, enthalpy with the symbol H. Therefore, for a system at constant pressure, * Increase in enthalpy (AH > 0) Heat is absorbed by the system (endothermic) * Decrease in enthalpy (AH <0) Heat is released by the system (exothermic)16 Materials Thermodynamics with Emphasis on Chemical Approach For changes at other than constant pressure, AH stil has a definite value, but AMY # | a SN ey More about enthalpy Although enthalpy is defined as a matter of convenience because it often occurs in | thermodynamic discussions, it also carries its own physical significance. Suppose | that a system is newly created. The energy required for the creation of the system is the internal energy (U) of the system and an additional energy to provide room to place the system by pushing the surroundings (PV). Enthalpy is the sum of these ‘two energies Heat Capacity Heat capacity of a system is defined as the amount of heat required to raise one unit of temperature of a unit mass of homogeneous material, provided that no phase or chemical changes occur during the transfer of heat. Thus, when the temperature of a unit mass of a material is raised by AT by absorbing heat of. where C is the heat capacity For an infinitesimal change in T, [--4| Materials with large heat capacities, like water, hold thermal energy well - their temperature do not rise much for a given amount of heat transferred, whereas materials With small heat capacities, like copper, do not hold thermal energy well, and hence temperature rises quickly. Recall that heat q is not a state function, so that the change in 4 depends on the other variable, for instance, V or P, in addition to T. Therefore, Atconstant volume At constant pressure and, = dH — where Cy is the heat capacity at constant volume, and Cp is the heat capacity at constant pressureee aE te The First Law of Thermodnamics 0 ‘More about heat capacity Heat capacity is directly related to temperature, and in turn the temperature is the result of the average total kinetic energy of particles in material. Hence heat capacity must be closely related to the kinetic energy portion of the internal ‘energy of the material (recall that the internal energy is the sum of the kinetic and potential energies). Heat is transfer of thermal energy. Thermal energy is stored as kinetic energy and also as potential energy. This distribution of thermal enerey contributes {0 the heat capacity. The more thermal energy goes to the potential energy, the higher the heat capacity is, Material “+f Directly related to temperature > Not related to temperature KE: Kinetic energy PE: Potential energy ‘The variation with temperature of the heat capacity, Cp, for a substance is often given by aan expression of the form: CpaatoT ter? where a, b and c are constants to be determined empirically Some examples, =106.6+17.8x10°7-28.5x10°T, J mot'K™" Cprcoyg) = 44-14+9.04x10° 7 ~8.54x10°T, J mol 'K™! (1) Prove the following statements: (@) AU and AH are usually very similar to each other for processes involving solids or liquids, (0) If gases are involved in a process, these may be significantly different. (©) Derive the relationship of Cy and Cp for an ideal gas. (2) Ifa reaction involves an increase of 1 mole of gases in the system, calculate the difference AH - AU at 298 K.8 Materials Thermodynamics with Emphasis on Chemical Approach (2) (@) PV work of condensed phases is normally negligibly small AH=AU+ APY) = AU (82) | ¢ (aH “var, | “\ar), = (©) If gases are involved in a process, ‘AH=AU+A(PP) PY@ORT a= AU + MRT = AU+ APY) |For perfect gas ANS AU + acnRT | ‘Therefore, if there is a change in the total number of moles of the gas phase, AH may be significantly different from AU (©) For ideal gases, H=U+RT Differentiating dH = dU + RaT U=AD only for ideal gases. | R aa a at Cp-G =R (2) AH - AU = A(n)RT = (1)(8.314 J mot! K")(298K) =2.48 kJ mol { eampte 2.9} Cp and Cy for argon gas are Cp = 20.8 J mol'K" and C; = 12.5 J mol'K"! Caleulate Co- Cy ,and discuss significance of the value calculated.FR + RP The First Law of Termodbnamies 9 Cp- Cy= 208 - 12.5 = 8.33 mol'K. This value is very close to the gas constant R, which verifies the relationship Cp C; ‘Substances usually expand with increase in temperature at constant pressure. Is Cp usually larger than Cy? ‘When thermal energy (heat) is supplied to a substance, ‘All the heat supp produces arise in temperature. Part of the heat may bbe used for work of ‘volume expansion, Therefore, C, is large than C,. More rigorous analysis: from the defi of Cp and Cy.’ Materials Thermodynamic with Emphasis on Chemical Approach Cy ar ov ),(ar), m4 ‘The contribution to Cp through the cchange in the volume of the system ‘due to the increase in temperature against the constant external pressure. —<— ‘The contribution from the energy required for the change in volume against the intemal cohesive forces acting between the constituent particles of a substance, For liquids and solids, which have strong internal cohesive forces, the term (QUIQV)> is large. For gases this term is usually small compared with P. An ideal gas is a gas consisting of non-interacting particles, and hence this term is zero. (@UIAV); = 0 for ideal gases x PV = RT Example 2.11 (ramped y In reversible, adiabatic process of a system comprising of one mole of an ideal gas, prove the following relationships: aU= bw Cyd = -PaV (1) dU = & + 6», but & =0 in an adiabatic proces. aU = 8 @ aU = CyaT bw =-Pav Cra Pav From this equation, a useful relationship can be derived, as given below:The First Law of Thermodynamics 2 LJ (ny ny T, Vy BV = PsV] = constant Example 2.12 For reversible adiabatic expansion of an ideal gas, we have seen PV" =c (constant) When a system comprising of one mole of an ideal gas changes its state from (P1.V;.T,) to (P2.V2T2), prove that work done by the system is we BRAM cot.)2 Material Thermodynamics with Emphasis on Chemical Approach Pi¥,- AY y-1 For an ideal gas, PY = RT and knowing Cp- Cy = R, and C/Cy= w=G(h A) Example 2.13 Phase transitions between solid and liquid, and liquid and vapor involve large amounts of energy compared to the heat capacity. The diagram below shows schematically the change of temperature of H,O as heat is added ata given pressure ‘When phase changes (jce-to-water and waterto-vapor) occur, the diagram shows plateaus, ie., the temperature stays unchanged until the phase changes are complete even though heat continues to be added. What is the role of the thermal energy added during the phase transitions? ‘Adétion of energy >ce i EE Oc The Fist Law of Thermodmamics B ‘When thermal energy (heat) goes into material, one of two things can happen: The ‘temperature of the material rises, or the material changes the state. When ice is heated, its temperature rises until the temperature reaches the melting point (the transition temperature from ice to water). ‘At the melting point (0°C), ice melts into water, but the temperature stays at 0°C until ice has melted completely. During the transition, the average kinetic energy of ice is the same as the average kinetic energy of water. Thermal energy absorbed does not go to the kinetic energy of the molecules (not speed up the molecules), but instead it is used to ‘change (loosen) intermolecular bonds and hence stored at potential energy which does not affect the temperature. ‘The energy required to change a liquid into the gaseous state at the boiling point is called heat of vaporization. This extra energy needed to turn water into vapor is used to break down the intermolecular attractive bonds, and also to provide the energy necessary 10 expand the gas (the PV work). Exercises 2.3 Metallic vapors generally have a monatomic constitution. According to the kinetic theory of gases, only three translational degrees of freedom need to be considered for monatomic gas and hence the translational kinetic energy is given by (1) Calculate AH when the temperature of 3 moles of the gas is raised from 700 to 100K. 2) Calculate Cy forthe gas. 3) Calculate Cp for the gas. 2.3 Enthalpy Change For a substance of fixed composition, the enthalpy change with change in temperature at constant pressure P can be calculated as follows: From the definition,Fry Materials Thermodynamics with Emphasis on Chemical Approach % AH J (a+ 67+ er )ar| i ‘The enthalpy change associated with a chemical reaction or phase change at constant pressure and temperature can be calculated from the enthalpy of each species involved in the process. When species A undergoes phase transformation from o: to B, Transformation" AH, = Haws) Har ‘The enthalpy change due to chemical reaction (AH) is the difference between the sum of enthalpies of the products and the sum of enthalpies of the reactants: AH = DH pres ~ Heats (Example) Fe,0;+2AI=Al05+2Fe: AM =(H,0, +2Hp.)-(Hpe,o, +2Ha)) Example 2.14 Pure copper melts at 1,084°C. Calculate the enthalpy change when 1 mole of copper is heated from 1,000°C to 1,100°C. (Crown = 31.4 J mol"K", Crows = 22.6 + 6.28 x 10° T, J mol'K", Heat of fusion (AH) : 13.000 J mot") Total enthalpy change = Enthalpy change associated with heating of solid copper to the ‘melting temperature +Heat of fusion at the melting temperature + Enthalpy change associated with heating of liquid copper to the temperature of 1,100°C.The Fist Law of Thermodynamics Fo 1,100°C Heating of liquid Co MM, = [Cp A #502 Imo! 1,084 Melting of Cu ‘AH, = 13,000J mot" bs Heating of solid Cu As CrrcynAT = 2,592 3 mot uns 1,000°C Heating (Addition of thermal energy) ‘Thus. the total enthalpy change: AM = AH, +AH, +AH, =16,094,3 mol” Example 2.15 Molten copper is supercooled to 5°C below its true melting point (1,084°C), Nucleation of solid copper then takes place and solidification proceeds under adiabatic conditions. Calculate the percentage of the solid copper. The actual path is not convenient | for thermodynamic calculations in this case, because copper solidifies during the process and the heat of fusion at temperatures other than the true melting point is not readil known, 1084 1079°C Path Instead, itis more convenient to take imaginary paths (1) Liquid copper is heated from 1,079°C to 1,084°C (Path 1): AH py > 0 (2) And then portion of the liquid copper solidifies at the true melting point (Path 2): AH pan <0. (3) AS the process is adiabatic, AM pani + AF pax = 0 ‘Since enthalpy is a state function, the enthalpy change along this imaginary paths should be the same as that along the true path. M yunt = J nee Crcun AT = 3141357 ~1352) = 157 J mol! 31.4) mot'k! AH py = -XBH, = 13000% Materials Thermodynamics with Emphasis on Chemical Approach ‘where x= fraction of copper solidified, and ‘AH, = heat of fusion of copper (13,000 J mol") ‘As solidification proceeds under adiabatic conditions, AH, Therefore, x = 0.012: fraction of solid copper { Example 2.16 —_—_—___———— ‘The reaction between methane and oxygen produces carbon dioxide and water vapor. Reaction path 1: CH, + 20; > CO; + 2H,0 Reaction path 2: CH, > C + 21 L__ 2H, + 0, + 2H,0 C+0; > C0. Prove that AH, + Ais + AH Because enthalpy is a state property, the enthalpy change depends on the initial and final states only, not on the path the process follows. As the sum of all the reactions in path 2 results in the same reaction asthe one in path 1, the enthalpy change should be the same for both paths. ‘The additive properties of enthalpy is known as Hess’s Law. According to this law, * The enthalpy change associated with a given chemical reaction is the same whether it takes place in one or several steps. + Enthalpies or enthalpy changes may be added or subtracted in parallel with the same manipulations performed on their respective components or reactions. ‘The above isin facta different expression of the state property of enthalpy Exercises 24 The melting point of CaTiSiO, is 1400°C and the heat of fusion at the normal ‘melting point is 123,700 J mor. Calculate the heat of fusion at 1 300°C. Crysis = 1774 + 23.2x10°T- 40.3x10°T, J mol'K™ Cris = 279.6 J mol'K" 25 Enthalpy changes resulting from temperature change can be represented on an enthalpy-temperature diagram as shown in the figure, Express on the diagram the answers to the following questions: Liquid (1) Enthalpy change when solid A melts at T., (2) Enthalpy change when liquid A is supercooled from 7,, to T;, and then solidifies. Solid (3) Enthalpy change when solid A is superheated AaT from T,, to 7; and then melts Ti+ SRR Chapter 3 The Second Law of Thermodynamics 3.1 Grades of Energy ‘Thermodynamics deals with energy. The first law is concemed with the conservation of energy in energy transfer. Energy may be transferred from one place to the other or transformed in one form to another, but the total energy of the universe (the system + the surroundings) is always conserved. [Now a question arises as to in which direction energy flows in a natural process, and if there is any law which governs the direction of the energy flow. Thus, the primary interest in thermodynamics is to predict the direction of chemical or physical processes, in particular the spontaneous, natural direction. Some examples we observe in our everyday life are, + Energy always flows spontaneously from a higher temperature to a lower temperature, ‘but not the reverse (thermal energy). + Energy always flows naturally from a higher pressure to a lower pressure (mechanical energy). ‘Energy always flows from a higher voltage potential to a lower voltage potential (clectrical energy). Wood burns spontaneously in air if ignited, but the reverse process, i.e, the spontaneous recombination of the combustion products to wood and oxygen in air, has never been observed in nature (chemical energy). ‘Ice at 1 aim. pressure and a temperature above 0°C always melts spontaneously, but ‘water at 1 afm. pressure and a temperature above 0°C never freezes spontaneously in nature (phase transition). ‘There will be numerous examples of processes which proceed in one direction, but not in the other direction spontaneously. The above examples strongly support the view that energy contained in the source fom which the energy is drawn must be different in ‘quality or grade from the energy contained in the sink into which the energy flows.8 Materials Thermodynamics with Emphasis on Chemical Approach ‘Thermal energy in water Suppose we have two buckets of water of the same amounts, but one at temperature ‘of 90°C, and the other at 40°C (Refer to the figure below.) Now thermal energy (heat) (Q) is taken out of the hot water by cooling from 90°C to 80°C (AT = -10°C). ‘The energy so extracted is transferred to the cold water, and heats the cold water from 40°C to 50°C (AT = +10°C), assuming that there is no heat loss and the heat capacity cof water is constant. The energy Q which was originally in the hot water is now in the cold water. Here a question arises as to whether it would be possible to let the same amount of energy Q return to the hot water spontaneously so that the temperature of the hot water recovers its original temperature, 90°C (AT = +10°C) ~ see the following figure. Our everyday experience disproves it. If it were the case, the hot ‘water could get hotter while the cold water becomes colder. Even though we talk about the same amount of energy Q, say, 1,000 joules, the energy in the hot water and that in the cold water are different in terms of ability or usefulness. This example clearly reveals that energy has quantity, and also quality as well Tee) Tee) B7o AB) 760) @ Te) 4 + 50} It would be very useful if we could find a function or property of a system by which the ‘quality (or grade) of energy is quantitatively determined. As it determines the direction of its flow, the energy grade of a system must be a function of the thermodynamic driving forces of the system which provides the impetus for the transfer of the energy from the system. When the thermodynamic driving forces in the system decrease, the energy in the system is degraded. In this regard, the energies contained in the sources in the above examples are atthe higher energy grades than those in the sinks. For example, the energy contained in a higher temperature system is at the higher energy grade than that in a lower temperature system. ‘When two systems exchange thermal energy in the mode of heat, the energy grades of both systems will be changed. Suppose two systems at different temperatures are placed in contact with each other. Then thermal energy will be transferred in the mode of heat from the high temperature system to the low temperature one. The following diagram schematically represents the changes of the energy and temperature of the systems:Seeietiasaanial The Second Law of Thermodynamics » ~ System A (high temperature) and System B (low temperature) are brought into contact with each other. ~ As the thermal energy is transferred, rn System A experiences decrease in the | amount of energy and also its temperature, 1 4 | whereas in System B both the amount of r po energy and its temperature increase. f ~ The transfer of thermal energy continues until the temperatures of both systems ‘arrive at the same temperature of 7°. - During the thermal process, the energies of both systems change: System A | { System 8 URTR UB. TS System A: UX Uy U5 (energy loss) UU, TR System B: US > Up — Us (energy gin) ~ According to the first aw, the energy loss of System A is equal to the energy gain of System B, and thus the total energy is conserved: Ug +U5 in tUp =U5 +U5, ‘The temperatures of both systems change: SystemA System B Ranoreh «Te (decrease) (increase) - Note that the energy in System A has experienced decrease in quantity and also in quality (grade) as the temperature of A has decreased, whereas the energy in System B is increased in quantity and also quality - The net effect of the above heat transfer process is that the total energy is conserved, but System A has left with a permanent degradation of its initial energy. The energy in ‘System B has been upgraded, but the so-upgraded energy is not useful (or available) for the purpose of returning the so-degraded energy of System A back to the level of its initial quality. The only way to bring the energy grade of System A back to the initial value by means of thermal energy is to transfer energy from a system which is at the temperature higher than 72. From the above example it can be concluded that, ‘the increase of the energy grade or energy quality of a system by heat transfer is possible, but only at the expense of lowering the energy grade of another system whose ‘energy grade is higher than that ofthe system, and0 Materials Thermodynamics with Emphasis om Chemical Approach * the so-upgraded energy of the system is of no use for recovering the energy grade of the other so-degraded system, and. ‘the universe (the sum of both systems in the present case) has suffered from a permanent degradation of the energy. ‘Thermal energy (Q) released from System A by cooling can be transferred to System B directly and thus raise the temperature of System B. ‘Thermal energy (Q) released from System B by cooling cannot be transferred to System A directly and is ‘unavailable for raising the temperature of System B. ‘Through the above discussions, it is now clear that factors which determine the extent of cchange in the grade of energy of a system is not just the quantity of energy transferred, but also the femperature of the system at which the energy transfer occurs. Consider the following example in which thermal energy is transferred by heat flow.The Second Law of Thermod namics u ‘Thermal energy q is to flow in the mode of heat from the hot body to the cold body. The heat flow may occur either (1) directly from the hot to cold bodies, e., Path 1, or (2) from the hot to warm, and then to cold bodies, ie., Path 2 + Path 3 “The degradation or decrease in quality of the thermal energy q is greater in Path 1 than in Path 2, as in the latter path further degradation should occur through Path 3 to reach the ssame final state. Thus, * Degradation in Path | > Degradation in Path 2 + Degradation in Path 1 > Degradation in Path 3 In other words, Path 1 is more irreversible than either Path 2 or Path 3. From the view point of the conversion of thermal energy into work (w), the above analysis can be interpreted as follows: + Once the thermal energy q is transferred to a lower temperature, sy, from T) £0 Ts it loses the capacity 10 do work which might have been done if a chance were given uring the course ofthe transfer. * The loss of capacity to do work is greater in Path 1 than in Path 2, as, after Path 2, there is a chance to do work during further cooling from 7; to T; (Path 3). * The loss of capacity to do work and the degradation (or decrease in quality) of thermal ‘energy shares the same origin; that is, the transfer of thermal energy. ‘Therefore, the quantification of degradation of thermal energy or the loss of capacity to do work must include both the amount of thermal energy transferred in the mode of heat, 4g, and the temperature T at which the transfer occurs. * The larger the amount of heat flow, the greater the extent of degradation, * The lower the temperature of the body to which heat flows. the higher the degree of degradation Extent of degradation = a | ‘Example 3.1 ‘Therefore, ‘Thermodynamics may be defined as a physical science concerned with the transfer of, heat and the performance of work accompanying various physical and chemical processes. The first law of thermodynamics is the law of energy conservation. Explain, using an example, why the first law is not enough to answer the following comments: “Some things happen spontaneously, some other things don’t.”2 Materials Thermodynamics with Emphasis on Chemical Approach Refer to the following two figures: Surroundings Bamoundnge Tow ‘ U | [system] | Taw | Tye Toae | “he proces stifin AU= q+ w.and The prcrasaain AU= + but rca spontaneously aided by sno cer spntnecl ea be aro indicated bythe wows ‘The above example demonstrates that the first law of thermodynamics alone is not enough to completely deal with processes which occur naturally. We now search in several different ways a function or property which can be a barometer of the direction of ‘a natural or spontaneous process. 3.2 Heat Engines and Entropy ‘A heat engine is a device for converting heat (thermal energy) into work (eg., steam engine, internal combustion engine). The figure on the right is the schematic representation of a heat engine ‘Each cycle takes thermal energy of heat (g,) from the high temperature heat reservoir, and ‘uses some of it to generate work (w), and ‘rejects the unused portion (ga, thermal energy) to the low temperature heat reservoir Heat reservar The efficiency of the engine is defined as ‘The amount of thermal energy expended to conduct work ‘The amount of thermal energy supplied to the engine Where “| "is to ensure € to be positive, ‘The prime interest we may have in dealing with a heat engine is to know the maximum amount of work that can be obtained from each cycle of the heat engine. We already know that the maximum work can be obtained when the process is conducted in a reversible manner (refer to Chapter 2.1). It is possible to devise a cyclic process which consists of processes which are all reversible.am SER te eo ‘The Second Law of Thermocbmamics 3 Carnot Cycle ‘The Carnot cycle is the cyclic operation of an idealized (ideal gas) engine which runs in four steps: wo reversible isothermal steps and two reversible adiabatic steps. After ‘completing a cycle, the system returns to its initial state so that all of the state functions restore their intial values. The figure below shows the Carnot engine, in which heat q, is taken in from the high temperature heat reservoir, work w is done through running a complete cycle of the ‘Carnot engine, and heat gis rejected to the low temperature heat reservoir. Heat Reservoir (high temperature) One cycle of the Carnot engine tis clear from the figure that work is done by the Camot engine through Step I and Step 2 as the gas expands, and work is done on the engine through Step 3 and Step 4 as the ‘gas is compressed. The net amount of work (w) done by the engine is the balance of the ‘work done by the engine and the work done on the engine. Now we discuss each step of the Carnot cycle one by one, ‘Step 1: Reversible isothermal (7) expansion: | = area (abba) = fray BIBLIOTECASo Materials Thermodynamics with Emphasis on Chemical Approach “The engine takes heat gy from the high temperature (T;) heat reservoir, and the gas in the engine expands isothermally and reversibly. The figure shown above explains how to ‘obtain the amount of work done by the engine in Step 1 Since the gas is at the constant temperature T,, the internal energy (U) stays unchanged: This is the amount of heat taken in from the high temperature heat reservoir to do work ‘wy by the reversible isothermal expansion. Note that in this isothermal expansion the temperature ofthe gas is the same as that of the high temperature heat reservoir (71) Step 2: Reversible adiabatic expansion: ‘The engine at this step is now insulated so that no heat is allowed to be exchanged with the surroundings. The gas expands from V3 to Vs and the pressure changes from P: to Ps, as depicted in the figure below. Since the expansion is conducted under the adiabatic condition, the temperature of the {gas decreases. The expansion continues until the temperature has become the same as the temperature ofthe low temperature heat reservoir (71). For the adiabatic change of the gas. the relationship of PY = nRT does not hold, but instead the relationship of = (constant) applies (see Example 2.11), ” pav P| i PVt= \ Work (w: area (b = f; PdV ieseoeras The Second Law of Thermodhnamics 38 This is the work done by the engine through the reversible adiabatic expansion, From the ideal gas law, we know the relationships of P. thus the last equation becomes AU =q+w |AU, = nC ,(T,-T,) ART; and PsV3 = nRT;, and. = 0 (adiabatic) ‘As can be seen above, by the reversible adiabatic expansion, the engine does work w: against the extemal pressure, and accordingly the intemal energy decreases by AU: and the temperature of the gas decreases from T; to T>. In order to bring the engine back to the initial starting point, the gas which has expanded through the above two steps must now be compressed to the initial volume. Step 3: Reversible isothermal compression: PV =nRT, cae ae Work (v3) = area dee) py, vey =n36 Materials Thermodnamics with Emphasis on Chemical Approach This is the amount of work done on the engine through the compression of the gas. Since the gas is at the constant temperature T;, the intemal energy (U) stays unchanged: AU, =0 This is the amount of heat (g; < 0) rejected by the gas to the low temperature heat reservoir. Note that in ths isothermal compression the temperature of the gas isthe same 4s that ofthe low temperature heat reservoir (73). Step 4: Reversible adiabatic compression: Now the engine is insulated again so that no heat exchange with the surroundings is allowed. The gas is compressed from V, to V; and the pressure changes from Py to P; ‘The process is graphically represented in the figure below. Since the compression is conducted under the reversible adiabatic condition, the ‘temperature of the gas rises. The compression continues until the temperature of the gas reaches that of the high temperature heat reservoir (73) which is also the temperature of ‘the gas at the beginning of the cycle. As seen in Step 2, for the reversible adiabatic change of the gas, the relationship of PY = nRT docs not hold, but instead the relationship of PV = c (constant) applies. Ina similar way to Step 2, my =nCy (Fj ~Ts) AU, = nC p(T -T.) As seen above, by the reversible adiabatic compression, the work ws is done on the‘The Second Law of Thermodmamics a ‘engine against the internal pressure, and accordingly the internal energy increases by AU, and the temperature of the gas rises from T; to 7) ‘The complete Carnot cycle is summarized in the following figure: ‘Step 1 e Isothermal i expansion, a Cars Aciabatic expansion Toh |p 25.7, Be avs = ‘fd @ insulation Isothermal compression, a Ina complete cycle, the gas follows the path “abed”. During the cycle, «noi feat en nom eh tempers = 2 ¥, + the amount of heat rejected to the low temperature heat reservoir: 4, = nT, In * the amount of work done by the engine: way twp twy ty, vy emer nB |g =)38 Materials Thermodmamics with Emphasis on Chemical Approach ~a, +a) For further consideration on the last equation, let us conditions given in Step 2-and Step 4. For Step 2, A 2 BA [ar =ner. 315 =ner, For Step 4, ina similar way, This last result is useful to bring @ very important relationship when it is combined with 4 and gz in the Carnot cycle Warenba s ¥, % = MRT, InP p= MRT, In | 4 7 = MRT, Inc DyBeo Th= The Second Law of Thermodynamics 2» ‘This equation is resulted from the reversible cyclic heat engine which is a closed system, in which heat; is taken in at T; and heat q is removed at 7, both of which are under the isothermal conditions. Since the sum of changes of any state property must be 2ero in a eyelic process, this last equation suggests that there exists a state property which is related to g/T. The change of this property during the expansion is qy/T; and its change ‘during the compression is qx/T. and the sum of these two changes for a complete cycle is zero, which is the necessary and sufficient condition for a state property. This property is termed entropy. The concept of entropy will be further refined after discussing the efficiency of the Carnot engine «¢ = The amount of thermal energy expended to conduct work __| »| cae ised ergs cedt Reeages ey w= +92) eats 4 This is a remarkable result: The efficiency depends only on the temperatures of the reservoirs, and is independent of the nature of the engine, working substance, or the type of work performed. ‘The above two equations indicate that only a fraction of the heat taken in from the high temperature reservoir is converted to work. This fraction is Nt oT 4 i It is obvious from the above relationship that complete conversion of heat into work is possible only if gz is equal to zero which means that T; is equal to OK, and thus it indicates that the complete conversion of heat into work is impossible in practice. Refer to the diagram of the Carnot cycle in the text. An engine operates between 1,200°C (T,) and 300°C (7;), and Step 1 (isothermal expansion) involves an expansion where the pressure of the gas drops from 6x10°N m? to 4x10*N m?. The ‘working substance is one mole ofan ideal gas. (1) Calculate the eficiency ofthe heat engine (2) Calculate heat absorbed in Step 1. (3) Calculate the amount of heat rejected in Step 3 (isothermal compression).0 Materials Thermodynamics with Emphasis on Chemical Approach T,=1473K 73K S11 or 61.1% @ @) Entropy Let us return to the important relationship obtained for a reversible cyclic process: ah. aa Since the heat exchanges are conducted reversibly,The Second Law of Thermodbnamics a If heat exchanges are conducted in an infinitesimal amount, Suz 9 qh Since the operation is a cyclic process, | $ os ‘This last equation applies not only to the Carnot cycle, but also to any cycle which is reversible (later in Example 3.5 we will see that this equation is equally valid for any { cyclic process which includes irreversible steps). A reversible cycle can be approximated by a series of Camot cycles as seen on the right in the following figure. In the figure, a number of curved lines are drawn for the isothermal and adiabatic processes. The entropy change of each step of individual Carnot cycles is cancelled by the neighboring Camot cycle, except all outmost steps indicated by thick lines in the figure. The sum of the entropy changes of these surviving steps must also be zero. The approximation can be close enough to the real arbitrary cycle by ‘making the individual Carnot cycles infinitesimally small ‘The eycle approximated by a series of Camot cycles A real cycle | _ tick zigzag curves) N ay > | : So far we have dealt with a cycle which is combination of reversible steps only. ‘However, itis reminded that the equation in the above is equally valid for a cycle which \ involves irreversible steps. This is discussed in Example 3.5,2 Materials Thermodynamics with Emphasis on Chemical Approach Now it is in order to examine whether or not each term in the above equation, ie. Girov/T, represents the change of a state property of the system. If it is really the case, its value for all processes which share the same inital and final states must be the same, irrespective of whether the process is reversible or irreversible. ‘The following figure shows two reversible cycles, ie., cycles “1a2r1” ind “Tbr” i v Combination of the above two equations yields, | CF) -0#) In the above equation, both integral terms indicate the change of the property. g/T, when the state is changed from State I to State 2 in the figure. The term on the left side is the change along the path “142” and the term on the right side is along the path “Ib2", and both are the same. This result ensures that the quantity of q/T for a reversible path is independent of the choice of the path as long as the initial and final states are not altered Thus it is a function of the state. In other words it is the change of a property of the system. This property is termed entropy withthe symbol of S. [=-8] Since the entropy is a state function, its change for a path must be the same irrespective of the path being reversible or imeversible. That is, the above relationship holds for both reversible and any irreversible processes, even though the equation includes 4, which is the heat flow for a reversible process (refer to Example 3.6 and page 77), Ifa system undergoes a change in state, say, from State 1 to State 2, the entropy change by the change of the state is given by integrating the above equation:re i eR FA R= RRR ee | The Second Law of Thermodynamics 6 ‘This equation can be integrated by expressing q as a function of T. Example 3.3 For a system which undergoes the process of the Camot cycle, calculate the entropy change of the system, the surroundings and the universe (the system + the surroundings). 1. Entropy change of the system (AS,,, ): (1) Step 1: Isothermal expansion : AS,, (Q) Step 2: Adiabatic expansion: AS,,.=0,a8q =0. (9) Step: Isothermal compression: AS, = 2 (4) Step 4: Adiabatic compression: AS, =0,a8 q = 0. Thus, a Spy = MS yy # Sea +S pgs + ASgg =A BE qt (see page 38) 2. Entropy change of the surroundings (AS,,,) (1 Sep: tera epson othe sytem: 8, = estos) (2) Step 2: Adiabatic expansion of the system: AS, =0 , as q = 0. (8) Step 3: Isothermal compression ofthe system: AS, = 2 (heat gain) (4) Step 4: Adiabatic compression of the system (AS,4-4): ASyrq =0 a8 9 =0. Thus, Sue = MSs + WSg2 + AS yup + Sup g =| 4 2) <0 3. Entropy change of the universe (AS) MS yy, = MS # AS uy =0 In summary, for a reversible cyclic process the entropies of the system, the surroundings and the universe all remain unaltered,bee Materials Thermodynamics with Emphasis on Chemical Approach Example 3.4 In the previous example (Example 3.3), when we consider the step of isothermal expansion only, what are the entropy changes of the system, surroundings and the universe? Se oes 1 eH) System Surroundings Isothermal expansion at 7, \_— Heat reservoir at 7) a Universe AS uni = AS yg + AS pur = 1k can be seen that the increase in the entropy of the system is exactly the same in numerical value as the decrease in the entropy of the surroundings, and thus, the total ‘entropy (the entropy of the universe) is unaltered. Inthe reversible process, thus, we may say that: Entropy of the amount of = has been transferred from the surroundings to the system. qT {exam te 85. J | An imeversble step is inserted into the Carnot cycle as show in the figure below. | The imeversible step added is an adiabatic free expansion. Determine the entropy changes of te system (the revised cycle), the surroundings and the universe. Assume thatthe working substance is n moles of ideal gas. Determine also the efficiency e On ‘Step A Rabati re expansion dP 7 Iothermal 7) compressa |The Second Law of Thermodynamics 45 ‘Step 1: Reversible isothermal expansion (ab) (1) Heat 5 a) = nk n> 0) ye Q) Work =nkh nL <0) - Sentins (3) Entropy change : AS, ponking Step A: Adiabatic free expansion (bb) (1) Heat an =0 (adiabatic) (2) Work wy =0 (free expansion) (3) Entropy change ~ The intemal energy does not change for an adiabatic free expansion (AU =9+w=0+0=0). ~ Thus there will be no change in temperature (Ti) ~ However, the entropy change is not equal to zero. We may find the entropy change by reversing the process since the entropy change for Step b’—b must be the same in numerical value asthe entropy change for the Step b+’, but in opposite sign The entropy is a state function, and thus we may choose the isothermal compression for Step b->b’ (Temperature: constant at 7). + AS, 4y =nRin A, and thus AS, = AS, 4y =nRIn Ye nh Ys Refer tothe further discussion given in Example 3.13, Step 2: Reversible adiabatic expansion (bc) (1) Heat q=0 (2) Work 1 My =nCy(Ty-T))(<0) (3) Entropy change : AS; =O since q =0, (Note that T = constant at 7; for adiabatic free expansion, but 7;—+7; for adiabatic reversible expansion.) Step 3: Reversible isothermal compression (cd) (1) Heat 7 =nRT, In“ (<0 in (20) (2) Work : j= MRT In“ 0) 9 nrinYs (3) Entropy change : AS, =. aR In—* (<0) a7 % Step 4: Reversible adiabatic compression (4~¥a) (1) Heat q=0“6 Materials Thermodynamics with Emphasis on Chemical Approach 2) Work Wy =nCp(T,-T,) (> 0) (3) Entropy change ; AS, =0 Entropy change of the system ( AS,,, : Total entropy change for the modified cycle) BS, =A FA, AS, 45,485 | ss, -mno(2) From the two adiabatic steps, ¥, % ; % (Refer to earlier discussion) —— | ASyx = nn =0 Recall that the modified cycle includes an irreversible step, but the entropy change of the system for the eyele is zero, This is another evidence that entropy is a state function, ‘Next, let us examine the entropy change of the surroundings. ‘Step I: Reversible isothermal expansion LN (1) Heat ine 4) = ART, In (2) Bnopy change : AS, = Ae = nk int Step A: Adiabatic free expansion (1) Heat dca (2) Entropy change: AS. Step 2: Reversible adiabatic expansion (Q) Heat Ge) 0 (2) Entropy change: AS; gy =0 Step 3: Reversible isothermal compression (1) Heat 1 Gee ™y = onRT, nh %na a On ‘The Second Law of Thermodyamics ” (2) Entropy change: ASs, ‘Step 4: Reversible adiabatic compression (1) Heat aur (2) Entropy change AS. uy Entropy change of the surroundings ( AS,,,) ASwur = AS yur + AS sur + AS, nn vs % From the two adiabatic steps, LA MS uni = AS pp + BS ur Sw nin 20) ‘The above analysis of a cyclic process may be summarized as follows: ‘+ The entropy change of the system (the engine) in a cyclic process is zero (no entropy change) irrespective of the cycle being reversible or irreversible, + The entropy change of the surroundings in acyclic process is zero ifthe entire process is reversible, but greater than zero if the process includes any ireversible step. *The entropy change of the universe in a cyclic process is zero if the process is reversible, but greater than zero if the process includes any irreversible step. Thus the entropy ofthe universe increases each time the cycle is completed The efficiency ofthe revised eyele: (1) Work done by the modified cycle (ws)6 ‘Materials Thermodynamics with Emphasis on Chemical Approach vy mts Cy)» tn! + G1 enarintes tn (<0) (2) Heat ken nom the suromiigs (59) Vs = 4 =ART,In“® (>0) ays = = MRT; Ir % 0) (3) Efficiency of the modified cycle: (e) Gore tgs = RT, In Ah + (nRTy In A= nT nL) + nT V%, % % %, 4% we know —2 =—3 = moh ¥, Then Wig =n in (7, ~ ys a Va>Vyand Va> Vi ‘Thus the second term on the right side is positive ate Le e< Em ‘The above result demonstrates that the efficiency of a cyclic engine which involves an irreversible step is lower than that of the Carnot cycle in which all steps are reversible.| ARES Po NR ne tore The Second Law of Thermodhnamies 0 ‘That is, the efficiency of the Camot engine is the maximum that a cyclic engine can ‘obtain, and all practical engines which involve irreversible step(s) have efficiencies lower than that of the Carnot engine, ! xxample 3.6 Let us consider a partial process of the Carnot cycle as shown in the figure below. The process starts at State “a” and ends at State “c” via States “b” and “b” Determine the entropy changes of the system, the surroundings, and the universe. Oy meee Ree tree expasion r Pats) (Pa) Alabaisompreton 2 SF expansion © (Ps) dePv teterml 7 comps From the results in Example 3.5, Us ¥, ¥ IS ine = MR INA 2 = nRin— (=, — Hh ning TE MSc) %, ¥, Se = ARIMA Gf, BS pep =n In a In Oh Su A Vy AS = Riz 0) Note from the above result that the entropy change (increase) of the system is the same for both the reversible and irreversible processes, whereas the entropy change (decrease) of the surroundings for the irreversible process is less than that for the reversible process. ‘The net result is that the total entropy, ie, the entropy of the universe, increases due to the irreversible step involved. The entropy change of the system can be viewed as follows: Envopy change | _ [_Envopy wansorea Entropy produced (generated) of the system. = | from the surroundings | * inside the system (ASyp) (Rin. (Rn ‘The sum is always the same as the entropy change for the reversible process.The Second Law of Thermodynamics st Example 38 ‘A Camot engine can be run in reverse and used to transfer energy in the mode of heat from a low temperature reservoir to a high temperature reservoir. ‘This type of a device is called a heat pump. if itis used as a heat source. It is called a refrigerator, if itis used to remove heat rove that, either for heat pump or for refrigerator, ‘work must be done on the engine. Heat reservoir Heat reservoir h Just as for a Camot engine running in the forward direction we have an engine running in the reverse direction. Fora complete cycle From the first law AU=(q\+4:)+w=0 : ean (er (1-2) T 1-t>0] <0 n?0| # w>0 | Work is done on the engine ‘The coefficient of performance of a heat pump (n) is defined as éThe Second Law of Thermodynamics st ‘A Camot engine can be run in reverse and used to transfer energy in the mode of heat from a low temperature reservoir to a high temperature reservoir. This type of a device is called a heat pump, if itis used as a heat source. It is called a refrigerator, if it is used to remove heat. Prove that, either for heat pump or for refrigerator, work must be done on the engine. Just as for a Carnot engine running in the forward direction we have an engine running in the reverse direction. For a complete cycle 4 <9 Th From the first law AU=(q+q)+w=0 w>0 | Work is done on the engine. € coefficient of performance of a heat pump (n) is defined as, la2 Materials Thermodynamics with Emphasis on Chemical Approach from the earlier discussion, Note that the coefficient of performance of a heat pump of a refrigerator, unlike the efficiency of a heat engine, can be greater than unity. Exercises 3.1 The following diagram shows the operation cycle of a Camot refrigerator. The refrigerator operates between 25°C (T;) and -10°C (7) and step 2 involves heat absorption of 500 J. (2) Calculate the coefficient of the refrigerator. (2) Calculate the total work done per cycle. Isothermal expansion‘The Second Law of Thermodynamics 3 3.3 Energy Dispersion and Entropy ‘Transfer of thermal energy induces degradation or decrease in quality of energy, which in tum results in the loss of capacity to do work. Natural or spontaneous processes always, cccur in the direction by which thermal energy is degraded. Entropy is not energy, but a kind of the measure of the amount of energy in a physical system not available to do work. However, the definition of entropy, AS = djy/7, which has been introduced earlier is in fact the definition of the change of entropy, not entropy itself. In order to define entropy itself explicitly, we need to consider the transfer of thermal energy in a microscopic point of view. Macrostates and Microstates Discussions so far have been based on macroscopic matter, and made no reference to the microscopic nature of matter. As we know that atoms or molecules of matter provide storage to the energy transferred to the matter, a question arises as to what happens in the matter in the molecular point of view when thermal energy has been transferred to or from the matter. To answer this question, we first define two important terms: ‘macrostates and microstates. Dictionaries define, “macro” as the prefix of the word “macroscopic” which designates a size scale very ‘much larger than that of atoms and molecules, and “micro-” as the prefix of the word “microscopic” which designates a size scale ‘comparable to the subatomic particles, atoms, and molecules. 3ut a macrostate and a microstate in thermodynamics do not just designate something big tnd small in size. In thermodynamics, a microstate isn't just about a smaller amount of natter or smaller size of matter, but it implies a detailed look at the energy that aolecules or other particles in a system have. ‘tus star our discussion with an example of a simple system: ‘uppose that there is a system consisting of three molecules and three units of energy to tare among them. The macrosiate of the system is the one having the physical size of sree molecules with the energy of three units. In classical thermodynamics, the acrostate is simply called the state. The macrostae or state does not care as to how the vergy is distributed among the molecules. As long asthe total number of molecules and e total units of energy are kept unaltered, the system is atthe same macrostate + forthe microstate, however, we need to look atthe energy distribution in detail, What » need to consider isthe number of ways the total energy can be distributed among the dlecules (or atoms). For the present example, there are several different ways of sributing these three units of energy tothe three molecules. One way is thatthe energy shared equally and each molecule has one unit of energy. The other way is that one slecule has all three units of energy and the other two have none. There is still another ¥: two units to one molecule, one unit to the other one molecule, and none to the last lecule. The following table shows all possible combinations.ss Materials Thermodynamics with Emphasis on Chemical Approach The system of (n=3,¢=3) No. of macrostates= 1 | No. of microstates = 10 Energy level Microstates Configurations ‘These ten possible combinations are referred to as microstates of the system. In other words, the system has ten different microstates and thus it takes one of these ten ‘microstates at any one instant in time. The specific phrase, “one of these ...at any instant in time” is important. The system cannot take two or more microstates at the same time, but only one microstate at a time. The system will be in one of the microstates at one instant, and in the next instant the system can immediately move to another microstate. ‘The system has 10 different choices for its microstate, but no options for its macrostate; i.e. itis under only one macrostate. The more number of microstates a system has, the more number of choices the system can take for the next instant. Let us consider more about the above system. First we define a “configuration” as the collection of those microstates that possess ‘identical distributions of energy among the accessible energy levels without distinguishing individual molecules. According to this definition of configuration, the system above has three different configurations. If all microstates are equally probable, the probability of any one configuration is proportional to the number of microstates: that is, the system will be at Configuration I for 10% of the time, at Configuration II for 30% Of the time, at Configuration III for 60% of the time AAs the number of molecules and the number of energy units increases, the number of accessible microstates will grow explosively: if a system has the size of 1000 molecules With the total energy of 1000 units, the number of available microstates will be around 10. a number that greatly exceeds the number of atoms in the observable universe. ‘A more rigorous definition of the microstate is; “A microstate is one of the large numbers of different accessible arrangements of the ‘molecules’ motional energy (the translational, rotational, and vibrational modes of ‘molecular motion) for a particular macrostate.” One microstate is something like an instantaneous snapshot of the energy of all the individual molecules in the macrostate. In the next instant the system immediately cchanges to another microstate. A single microstate of a system has all the energies of allThe Second Law of Termodsnamics 85 the molecules on specific energy levels at one instant. All of the energy of a system can only be in one microstate at any time. Energy Dispersion and Entropy ‘A macrostate is the thermodynamic state of a system that is exactly characterized by the system's properties such as P, V, T, and number of moles of each constituent. Thus, if ‘observable properties (P, V, T, ...) do not change, a macrostate does not change over time, but the microstate does. ‘The energy of a system becomes more dispersed when the number of microstates available to occupy, i., the number of accessible microstates, becomes larger - there are ‘more choices the system can take for distributing its energy at one instant. The bottom line is that the change in the number of accessible microstates is the determiner of the spontaneous direction of a natural process. Entropy is now defined to be the measure of the spontaneous dispersal of energy (in the previous sections it was called degradation of energy) for a system. As the number of ‘microstates that are accessible for a system indicates all the different ways thatthe energy can be arranged in that system, the larger the number of accessible microstates, the seater the entropy of the system at a given temperature. ‘The correlation of the entropy with the number of microstates is shown by the Boltzmann ‘equation which is one of the most celebrated equations in statistical thermodynamics: S=kinW where is the number of microstates, and k is Boltzmann's constant (1.38x107°J K"!), Then the change of entropy between two different states (the initial and final states) will be, ) n{ Mane W, nual ) How is this equation related to the following expression of the entropy change developed from the macroscopic approach of classical thermodynamics? asetn r These two expressions, the latter from macroscopic approach and the former from ‘microscopic considerations, are indeed related to each other, and the relationship is clarified in Examples 3.14 and 3.17. Why does 5 depend not on W, but on the logarithm of W? Suppose we have two systems: System 1 (entropy of S; and the number of microstates of W;) and System 2 ‘entropy of S; and the number of microstates of WW). If we now redefine these twowi 6 Materials Thermodynamics with Emphasis on Chemical Approach systems as a single system, then the entropy of the new system will be the sum of the two: 5; + S:. But the number of microstates will be the product HY;XIV; because for each ‘microstate of System 1, System 2 can be in any of HV; numbers of microstates. ‘System 1 ‘System 2 New System Sh 3% | }———-|[s.m [sm S\=khnif, — S)=kinthy S. W=We 32545 Saknw skint, | 5, =k, we, S=kinW,+kinW, Kin Ws) S=kin(WH) S=kInW, kin, Now the entropy expressed by the logarithm of 1” warrants the additive nature of entropy Provided that we are able to calculate the number of microstates for a given macrostate, the Boltzmann equation gives us answers to the relation between molecular motion and entropy of a system, e.,the relationship between Molecules (or atoms or ions) constantly energetically What we define as speeding, colliding with each other, moving distances its entropy of the in space (or, just vibrating rapidly in solids) system Se ane at) ‘Suppose that we have two hypothetical metal blocks: Block 1 having mass of three atoms and energy of 6 units, and Block 2 having mass of three atoms and energy of 2 units ‘There will be a number of ways of distributing the energy tothe atom in each block. The following diagram shows the number of ways of distributing the energy between the atoms, i. ,the number of microstates each block has: No nergy ranjer Block 1(n=3,e=6) > _ Block 2 (n=3,e=2) s ees 4 T W=6 5 aA ee | BH aol Ee t 2 : Bobet stem se ; t oleate te olan cone tt mw viv val |come| tt Tt [micro] 3761613131611] |atem|3 31 7 T * Config: configuration number, Micro.: Number of microstatesThe Second Law of Thermodynamics 7 Block 1 has 7 different arrangements (configurations) of atoms to the accessible energy levels, while Block 2 has 2 different configurations. Each of the configurations has its ‘own number of microstates. For example, Configuration I of Block | has three different ways of arranging three atoms in those two energy levels. Let us name the atoms A, B and C, then the diagram on the right shows three different arrangements. In this way we can find that Block 1 has 28 rmicrostates (W = 28) in total, and Block 2 has 6 (W = 6). If the combination of Block | and Block 2 is considered to form one system, but without allowing energy transfer between them, then the number of microstates of the system will be W = 168 (= 28x6), [Now suppose that one unit of energy is transferred from Block 1 to Block 2 so that the energy of Block 1 is reduced from 6 to 5 units, while the energy of Block 2 is increased from 2 to 3 units. Microstates of the two blocks in the new system are shown in the diagram below. The number of microstates of the combined system (Block I + Block 2) is now 210 (= 21x10), which is larger than that of the previous case where it was 168. Therefore, transfer of one unit of energy from Block 1 to Block 2 results in increase of the number of microstates, and thus the transfer must be spontaneous or natural, Energy ®O©.@OQ.@@) Block 1 (n=3,e=6—5) -E}+ Block 2 (n=3,e=273) ya weal | 4 {w= 10} 5 5 ape ado : Bao a 53 ; ay aa ne I | ae jane q = t oem cont] 1 tm WV cone] ttt lmera] 361633) lure] 3611) Further transfer of energy by one unit equalizes the energy of both blocks. The result is shown in the following figure: }+ Block 2 (n=3,. 3-4) w=is} {w= 1s} etree reves ig38 Materials Thermodynamics with Emphasis on Chemical Approgch ‘The number of microstates of the combined system is 225 (= 15x15), and thus this transfer of energy is also spontaneous. Further transfer of energy will not occur spontaneously as it will decrease the number of microstates because itis the reverse of the above transfer sequence. ‘The above results are graphically shown in the following figure: sopescunit JOON Microstates_| 168 | 210 | 225 | 210 | 168 | els [s|e | Block I { = Z w| 2% [2% [1s | 10] 6 «]213l14]s[e6 Sock 2 ao w wo | is | 21 | 28 Note that the number of microstates reaches the maximum when both blocks share the ‘same energy in the present case (i.e., the same temperature). No further transfer of energy ‘will occur spontaneously. Note also that the energy disperses to become uniform, through ‘which the number of microstates reaches the maximum. [As for the view of degradation of energy, let us look at the energy transfer again. For Block 1, it initially had 6 units of energy, but, after losing one unit of energy to Block 2, itis left with 5 units of energy. However, these S units of energy are not the same as before not only in the quantity of energy, but also in its quality. These remaining 5 units of the energy have been degraded, since these energies are not available for conducting all the work the initial 6 units of energy could do. ‘The energy in Block 2 has been upgraded by receiving one unit of energy from Block 1, but these upgraded energies are not available or useful for the energy of Block 1 10 recover its initial grade. It is not possible for Block 2 to return one unit of energy back 10 Block 1 on its own right. Ifit could, the number of microstates would have decreased, When we calculate the entropy of these three hypothetical systems, + Before energy transfer S=kim68 + After energy transfer by one unit: $= kin210 + After energy transfer by two ut In 25 (uniform energy distribution)‘The Second Law of Thermodynamics 2 It is clear from the above that the total energy disperses toward uniform distribution, ie., toward the maximum number of microstates, or toward the maximum entropy. In the previous discussion, we have seen that a particular configuration can have several different arrangements of molecules (or atoms) to the accessible nergy levels (microstates). Here we discuss in a systematic way as to how to determine the number of microstates for a given configuration. Consider the number of ways of distributing total n particles in a number of different energy levels in such a way that 1m particles inthe 9 energy level, 1, particles in the €, energy level, ‘my particle in the e» energy level, rn, particles in te €, energy level. Then the total number of ways to arrange m particles is n!, but there are, 1! ways of arranging my particles inthe é energy level: not distinguishable, 1 ways of arranging m, particles in the €, energy level: not distinguishable, ‘ml ways of arranging n; particles inthe e2 energy level: not distinguishable, ‘7! ways of arranging n, particles in the e, energy level: nor distinguishable. Therefore, not all n! ways are distinguishable, since the particles at a same energy level are merely changing their sequential positions at the same level. Thus the number of distinguishable ways of arrangements (the number of microstates) His given by Example 3.9 Five units of energy are distributed among three distinguishable particles. Calculate the total number of accessible microstates in the system. If E units of energy are distributed among 7 distinguishable particles, the total number of accessible microstates Wis given byo Materials Thermodynamics with Emphasis on Chemical Approach G+5-D! GIs! Example 3.10 Let us define the notation {a, b, c,.} in which the numbers from the left, a, b, represent the occupancy of the energy levels from the lowest one upwards. Calculate ‘the number of microstates for a system consisting of five energy levels in a state with ‘occupation of the energy levels (2.3,4,2,1). q a nl Ing! n= 2sBede241 = 12 Example 3.11 Caleulate the entropy of the system which consists of 12 particles in a state with cccupation of the energy levels {2.3,4,2,1). r= 1.38066 x 10) K" ‘S=1,38066%10" Jn(831,600)J K! =1.88x10779K" Example 3.12 A system consists of 10 particles distributed over four energy levels {5.3.20}. Ifa single particle is excited by one energy level, what would be the new distribution of Particles inthe energy levels which maximizes the entropy ofthe system?The Second Law of Thermodsnamics 6 Exciting a particle from the configuration {5,3,2,0} leads to the following three possibilities: {4.4.2.0}, {5,2,3,0} and {5,3,1,1}. Then, {44.20} 9 W = ‘The configuration which maximizes the entropy {523.0} W = is thus {5,3,1,1}: spreading out to the higher ‘energy level. (53,1. + ¥ = Example 3.13 In Example 3.5, an adiabatic free expansion step was inserted to know the effect of, ‘an irreversible step on the entropy change of the system. Although there was no heat transfer and no work done during the expansion, there was a change of entropy of the system. The entropy change was found in the Example by reversing the process; ie, ‘by compressing the expanded gas back to its initial volume. Explain the entropy change along with an adiabatic free expansion in view of the change in the number of microstates. ‘When the volume of a system is increased without change in energy, its energy levels become closer together, ie, more energy levels become accessible to molecules which are within the original energy range. Thus, while the original molecular motional energy is still the same in the larger volume (isothermal) the system has more energy levels, meaning that the number of accessible microstates increases. This can be conceptually proved by employing quantum mechanics. The energy (translational energy) fora particle in a cubic box is given by Wnt +n) +n) fea) where m is the mass of the particle, jis the Plank constant, m, and n. are the quantum numbers which can have positive integer values, and V’is the volume of the box. Upon expansion of the box (ce. inerease in F), the energy (€) of each quantum level, ie. a given (n, ,.7), decreases as can be seen in the above equation. Since the total energy of the gas does not change upon expansion into vacuum, the gap between the energy levels narrows as the volume expands, and thus more accessible energy levels are >rovided, leading to increase in the number of accessible microstates. (The following figure schematically represents the above discussion:o Materials Thermodynamics with Emphasis on Chemical Approach ‘Vacuum papel es Before expansion After expansion Accessible energy levels, 3.4 Equilibrium Criterion and Entropy Equilbirum Criterion ‘When a system is left to itself, it would either remain unchanged in its inital state, or ‘move spontaneously to some other state. Ifthe former is the case, the intial state is indeed the equilibrium state. Ifthe latter is the case, however, the system is initially in a ‘non-equilibrium state, and the system will spontaneously move to the equilibrium state. From the discussions done so far, we may be able to draw the following summary: + All real processes involve some degree of irreversibility and thus all real processes lead to an increase inthe total entropy: Sur = Sy + Sud AS > O. + The total entropy does not change in the reversible process (AS, = 0). + The reversible process is the succession of equilibrium states. + At equilibrium, the total entropy or the number of accessible microstates is maximum. ‘The total entropy isthe Sex Process path From the molecular point of view, the equilibrium state is the state at which thermal ‘energy is dispersed to the maximum: ie., a state at which the number of accessible‘The Second Law of Thermodynamics 6 :icrostates is the maximum. Therefore, the following is the condition to be satisfied for a state to be at equilibrium: ‘where Wis the total number of microstates (accessible) which was given earlier as, nl Tolman w= Recall that the number of microstates defined by above equation is in fact the total number of microstates for a given configuration, not for all configurations of the a system. Under what conditions can we assume the above equation to represent approximately the total number of microstates of the whole system? Suppose that we have n particles which are distinguishable from each other, but do not i imeract with each other. All n particles are | Lefthalf — Righthalf contained in a box. We are interested in the total i number of possible distributions of the particles in the box whether each of them is on the left or right half. The number of distributions may be called the number of microstates. If the total number of particles is four, then the statistics willbe like what we can see inthe following: is] Noof ‘Ramibr of micros Tet | Right | microsates | Prbebiity | | 93g os 7 Ta Ps a a6 22 € ai6 sma 4 a6 =o 1 16 Toad ig [ae Note that the curve is symmetric about the configuration of equal distribution (2 and 2).. Suppose that we now increase the number of particles to distribute, and the following is the selected statistics with 10 particles. Note that the smallest number of microstates is still unity as with less number of particles, but the largest number has grown to 252, and the plot shows much sharper peak at the configuration having equal number of particles in both halves (ce., uniform distribution), When we have 100 particles, the number of microstates of the most probable -onfiguration (equal distribution of 50:50) will explosively grow as given below:“ Materials Thermodynamics with Emphasis on Chemical Approach ides | No.of ‘Nonber of misrosatcs Tet | Rigit | microates | Prbsbiliy | so 199" 150.200" 250 300 o[ 10 T Tare 9 10 Toss aelaaa 45 457814 37 120 Toot 216 210, Diovsis sos 252, 2527814 [4 210, EIUIIEY rales 120. Tage 2 cc 457814 [1 10 ovale Too 1 sid Tour ua T For 1,000 particles, the number of microstates of the most probable configuration becomes to be 1000: Ww 10° 5001500! AAs the number of particles is increased, the number of microstates of the most probable configuration becomes dominating and virtually represents the total number of mace ‘The systematic way of finding the maximum number of microstates for a configuration, Which must be the most probable configuration, is to take derivative of the equation for the number of microstates and put it equal to zero: gh! w nn, =Number of particles atthe left half rng = Number of particles atthe right half ng =n-n, ond wat min—mp! | ‘Taking logarithm for convenience, InW = Inn’ Inn, In(n=n,)! Applying the Stirling's approximation, | Inn!=nlnn—nfor large nThe Second Law of Thermodynamics 6s 4 InW =nlnn=n, Inn, —(n—m, )in(n—m,) ‘Taking derivative with respect to m, m= | [nate] Now the procedure scen in the above example is extended to be applicable to more ‘general cases: ——— Wa" _ nginingham) ‘Taking the natural logarithm, InW = Innt~(Inngl+inny+ inn) | o in =Inn!—S lnm} Applying the Stirling’s approximation | In x!= xIn.x—x InW =(ninn— Zr inn) | raking dexivative, + dn =-L (nd Inn, + ind, ~dn,) anv =-Z(n +n) dW =-Slnndn,) Atthe maximum of WF, | dinIv =0Co “Materials Thermodynamics with Emphasis on Chemical Approach + Y(mndn,)=0 ‘This equation represents the condition for the maximum number of microstates of the ‘most probable configuration, and in fact the total number of microstates of the system, provided that » is sufficiently large. However, there are two constraints which must be met; (1) The total energy (U) must be constant Tne esr a] (2) The total number of atoms (or molecules) must be constant: fom | Sdn or inthe differential form | Sed, or in the differe Applying so-called the undetermined multipliers, Lltnnain,) =0 ‘Summation of these three equations yields, BY edn, =0 oS an, where o. and B are constant. Tlinn,+e+Be;)dn, =0 dn, +0 Therefore, Inn, +0.+Be, =0 Summation yields Combining the last two equations,‘The Second Law of Thermod)mamics This equation gives the number of particles (n,) which will be found at the energy level of ,,0F the probability (n,/n) that a particular particle will be found at the energy level of €, for the maximum number of microstates (J4), or for the maximum entropy (S = k In W), or at equilibrium (d In W= 0). Partition Function ‘The constant B introduced in the above equation is related to temperature and given as*, 1 ~ Readers who are ioterested in p= more discussion on this ae i ‘ggesed to refer to books on atistial thermodynamics, [ise ecynetes Sara where k is Boltzmann's constant: k =1.38x10"°J K" Substitution yields, "S Boltzmann distribution Definition of a function termed Partition function ‘The partition function defined above is the sum of all the energy states allowed. The partition function is a function of temperature T and microstate energies €,’s, and the microstate energies are determined by other thermodynamic variables such as the number of particles and the volume, as well as microscopic quantities like the mass of the 2onstituent particles. The partition function is a particularly useful function which allows 1s to calculate all the thermodynamic properties of the system, once it is known. Partition ‘unetion encodes how the probabilities are partitioned among the different microstates, vased on their individual energies. If all states are equally probable (equal energies) the ‘arttion function is representative of the total number of possible states. { Example 3.15 Suppose that we have a hypothetical system in which m atoms are distributed in two energy levels. Using the Boltzmann distribution, discuss the dependence of the sntropy change on 1/7, i6s Materials Thermodynamics with Emphasis on Chemical Approach According to the Boltzmann distribution, mid Ite ‘Then the distribution of atoms in level 1 and level 2 can be represented by the ratio of the ‘number of atoms in level 2 to that in level 1, which is given by Itis seen that the ratio is dependent on the temperature. If the temperature approaches OK, the ratio becomes zero, meaning that n; = 0 and thus all atoms are in the ground state (evel 1). On the other hand, if the temperature is increased very high, the ratio approaches unity, which means the atoms are evenly distributed between the two levels. As the temperature is increased, therefore, more particles are accessed to the higher energy level, and thus the number of accessible microstates increases, and then the ‘entropy of the system increases. It can be said that the entropy is a kind of function of the (3) mJ Suppose we have two systems; one at a cold temperature T-, and the other at higher temperature 7), both of which have two energy levels and n atoms. Then, the ratios (hs) are given by(2) mds, When the two systems are placed in contact with each other, the temperature will be ‘equalized to the equilibrium temperature (T,). T+T, Then, Let us assume that Tis higher than T. by o. times, that is, 7, = ctT; a da, ‘The number of microstates of the high temperature system will decrease by cooling from T, to T,, and on the other hand the number of microstates of the cold temperature system. will increase by heating from T. to T,. The ratio of the microstates at 7, to that at T, of the high temperature system will be given by, ka je fr (ey da, aah 1% According to the Boltzmann equation for entropy, the entropy change due to the change in state is proportional tothe logarithm ofthe ratio of the number of microstaes of the initial and final states. Thus the entropy change by changing the temperature from T 10 T, will be proportional to the logarithm of the above equation’ h |e iy, \or+oy Jer, “he above equation clearly predicts that the entropy change is inversely proportional to he temperature for a given temperature difference (j.e., for a given @). The above uation also predicts decrease of the entropy upon cooling, since the value of 0. is reater than unity. In a similar way, for heating of the low temperature system to the 3uilibrium temperature,0 Materials Thermodynamics with Emphasis on Chemical Approach € (ake Note in the above equation that it predicts that the entropy is also inversely proportional to the temperature for a given temperature difference and it increases upon heating. The cchange of the total entropy may also be predicted by adding the above two equations: te nt (1a \2 (o-1)e _((o-t") e , Pies (as)t (ze (ele ° ‘The above proves that heat transfer always results in increase of the total entropy of the tuniverse (for the present case, the sum of the high temperature and low temperature systems), ‘The macrostate (or simply state) of a system can be fixed by fixing some of the variables like U, V, m and T. Not all of them are independent. When we fix V and n, for instance, U is dependent on T. Express internal energy in terms of partition function, aaze™ | Eee Taking derivative a er | Multiplying tooth sidesThe Second Law of Thermodynamics n Example 3.17 Express entropy in terms of partition function, Make use of the results obtained in the previous example. Recall In =nlnn—In,lnn, wd Combining the two equations, In =ninn—ninn+ninZ+—™ NATn Materials Thermodynamics with Emphasis on Chemical Approach t InW =ninZ+ 7 NAT wenare( 42) aT hw S=kinv Senkinz «ntr( #82) a )y Per mole of particles, senatnz-encir[ Classical thermodynamics defines the change of entropy a system by daz) ” Statistical thermodynamics, on the other hand, defines entropy by dS=kdinw Discuss how they are related to each other. From the previous example, NAT InW=nnZ+The Second Law of Thermodynamics a For constant temperature, din = —"— du NAT N, watay dinw = iT dU = da, at constant volume dinw = Mm aT kd inw ~ Tews T dS = kd iInW dq, From statistical a : ermocnemice Fw clanial decmiannles 3.5 Entropy Changes and Entropy Productions If we are faced with the problem of deciding whether a given process will proceed ‘spontaneously, we might intuitively think whether there is enough energy available. We ‘might suppose that itis pethaps the energy of the system that tends to become minimum and then would be tempted to suggest that, + ifthe reaction is exothermic (AF <0), it takes place spontaneously, and. ~ ifthe reaction is endothermic (AH > 0), it does not take place spontaneously. Aowever, there are numerous reactions that are endothermic (heat absorbing), and occur spontaneously. For example, the phase transformation of white tin (Sn) to gray tin is ‘xothermic: Sn(white, 298K) = Sn(gray,298K) AW= ‘ut white tin is more stable at 298K. Thus energy alone then is not sufficient, snother example is dissolution of solid NaNO; in water. It dissolves, even though the rocess is endothermic (A> 0). 100 J mor"4 Materials Thermodynamics with Emphasis on Chemical Approach Moreover, if the energy of the system decreases during @ spontaneous change, its surroundings must experience increase in energy by the same amount in order to satisfy the first law of thermodynamics. This implies that the increase in energy of the surroundings is also spontaneous. Therefore energy alone does not provide a decisive clue as to whether or not a process of interest is spontaneous. Entropy Changes In order to clarify how a system changes of its state, we need to know not only the ‘amount of energy in the system, but also the direction of distribution of the energy. We already discussed that itis entropy that satisfies the requirements, and the entropy change was defined as, as= T Application of this equation is now discussed using a simplifed process. Let us consider a cylinder which contains water and water vapor at temperature T. The cylinder is in thermal contact with a heat reservoir, and they are in thermal equilibrium with each other at temperature 7. The system (cylinder) and the surroundings (heat reservoir) are schematically shown below: Frictionless piston t Now thermodynamic states of the above setting can be summarized as follows + The temperature inside the cylinder is the same as that of the heat reservoir at T. * The pressure inside the cylinder is the saturation vapor pressure of water at T(P,). * The external pressure (P.) is kept the same as the internal pressure P,,i.e.,P, = P, * The whole setting isin equilibrium and the piston does not move in either direction Next, the extemal pressure is suddenly decreased by AP, and thus the piston moves out due to the pressure imbalance (Refer to the following figure). After one mole of water has vaporized, the external pressure is restored to the saturation vapor pressure of water (Pp aT.The Second Law of Termodsnamice 8 During the above process, the following events will occur * The volume inside the eylinder expands and the internal pressure decreases + Water vaporizes and heat flows from the reservoir as the vaporization is endothermic. * The piston (ritionless) moves outwards and conducts work against the new external pressure (Pay =P - AP). + Afier one mole of water has vaporized, the system (cylinder: water + water vapor) and the surroundings restores the new equilibrium at temperature T and pressure P, ‘But the amount of water vapor in the system at the new equilibrium state has been inereased by one mole. Otherwise the system at the new equilibrium is the same as before (the same T and P). In the process described above, the system (cylinder) conducted work against the external pressure of Pz =P, ~ AP, and hence the amount of work done by the system is wah, aPy where V = molar volume of water vapor. The negative sign in the equation (i.e. the negative amount of work) warrants that the work was done by the system and thus the system has lost energy. ‘The amount of heat (thermal energy) transferred from the heat reservoir to the cylinder ccan be found from the first law; AU =q+w Thus, =U +(P,-aPy AS the reservoir (surroundings) has lost this amount of thermal energy as heat to the system, the entropy change of the surroundings (which is so large that its temperature virtually does not change by losing the heat of q) is given by, a5, =-4 for an infinitesimal change, Note thatthe entropy change of the reservoir (ASy,) is not constant, but varies with the segree of irreversibility; that is, it changes with change in AP- AU+(P-aP\y ip se the larger AP is, the less amount of work the cylinder (the system) performs, and the taller the amount of thermal energy the surroundings loses to the system, and thus the ‘naller the entropy change (decrease as q <0) ofthe surroundings becomes. Then the above process is conducted in a reversible manner by infinitesimally small range in P, i.e.,AP —> 0, then the above equation will become, Reservoir 7 ‘The entropy change of the surroundings as a function of the degree of irreversibility can bbe graphically represented as follows: When the process is conducted reversiby. Decrease in the degres of reversibility —» “sy Sur‘The Second Law of Thermodynamics ‘These are valid for any process, irespective of the process being reversible or irreversible, since the entropy is a state function. To help better understand the above equations as to why guy is used even for an inreversible process, we now analyze in depth the transfer of thermal energy in the mode of heat and the conversion of thermal energy into the mode of work. The figure given below explains the transfer of thermal energy in an arbitrary irreversible process: ‘Surroundings Yor w, _—————— ‘Thermal energy 4 | taken in from the surroundings (g) v ‘Thermal energy expended by conducting work Toe (Orda) If the process is conducted in a reversible manner, the transfer and conversion of thermal ‘energy can be represented by the following figure: Surroundings Thermal energy -— — rer }taken in from the surroundings (,) Thr x ay Renay Sree aU tint y ae ie ————~“1 {ote that, in the case of the reversible process both thermal energy taken in and that pended to conduct work are larger than those in the case of an irreversible process, but ve change in the internal energy, AU. isthe same as it isa state property ‘hen the above two processes are compared, Yer — Reversible process Goer ‘reversible process 7 ‘Thermal energy which Cone ‘could have done work, had ‘Thermal energy Which would have the process been reversible ben taken in from the surroundings, ‘but unused and left in the had the process been reversible (y,.) SYSTEM (fen)® Materials Thermodynamics with Emphasis on Chemical Approach ‘Two important points can be noted from the above: (1) Use ir * Usjtersev Since the internal energy is a state property. @ Irreversible process Reversible process proce: roces 9 * Gar = Gres ‘The thermal energy ‘The thermal energy The thermal energy transferred from the tunexpended, but left | | transferred from the surroundings Lin the system surroundings ‘The change of thermal energy which the system experiences in an imeversible process is ‘the sum of the energy transferred from the surroundings and the thermal energy ‘unexpended because of less amount of work done due to the process being irreversible, and the sum is always the same as the thermal energy transferred in the reversible process. ‘The following figure shows schematically the entropy changes of the system, the surroundings and the universe as a function of the degree of irreversibility [ Reverb | ath Gos adn AS eo SF {tis emphasized again that although the thermal energy appeared in the expression for the entropy change of the system is that for a reversible process, the application of the equationThe Second Law of Thermodsnamics ” is not limited t0 the reversible process only, but equally valid for any irreversible processes. The total entropy change is then, MS) = AS ps +S, AS Grey = Gmux and thus Gree 29 Thus, the entropy of the universe (the system + the surroundings: AS,, ) increases in itreversible (or natural, or spontaneous) processes. Only if the process is reversible, in other words, if the process is a succession of equilibrium states, the entropy of the tuniverse remains unchanged. In other words the entropy is merely transferred from the system to the surroundings, or vice versa in the reversible process. The entropy change accompanied by the change in state can be found by integrating the differential expression of the entropy change between the two limiting states: ‘Suppose we are interested in finding the entropy change due to the change in temperature from 7; to T; at a constant pressure, Then,Materials Thermodynamics with Emphass on Chemical Approach At constant P, pe, = aH dH = Cyd? | bas = Mocs Se ap State 1 = 7), State 2 = ‘The above equation allows us to find the entropy change of a material due to the change of temperature. Example 3.19 Entropy is defined as &q as2 St T for a system, where the equality sign holds for a reversible process and the inequality sign for an irreversible process. We know that 8y is not a state function, ie., it | depends on the path the process takes. Using the case of an ideal gas, prove that entropy isa state function. Consider one mole of a perfect gas. AU =8q +5] First law of thermodynamics ve ccap | 84% dar for a reversible process ance bw = - PdV for PY work CydT = dg... ~PaV PV = RT for one mole of a perfect gas AS = dpa/ Tby definition