Chemical thermodynamics : basic concepts and methods

著者

• Klotz, Irving M. (Irving Myron)
• Rosenberg, Robert M.

書誌事項

Chemical thermodynamics : basic concepts and methods

Irving M. Klotz, Robert M. Rosenberg

Wiley, c2008

7th ed

注記

Includes bibliographical references and index

内容説明・目次

内容説明

A completely updated, expanded edition of a longstanding and influential text on chemical thermodynamics Covers the logical foundations and interrelationships of thermodynamics and their application to problems that are commonly encountered by the chemist. Explanations of abstract concepts in a clear and simple, yet still rigorous fashion Logical arrangement of the material to facilitate learning, including worked out examples. Computational techniques, graphical, numerical, and analytical, are described fully and are used frequently, both in illustrative and in assigned problems.

目次

Preface xix 1 Introduction 1 1.1 Origins of Chemical Thermodynamics 1 1.2 Objectives of Chemical Thermodynamics 4 1.3 Limitations of Classic Thermodynamics 4 References 6 2 Mathematical Preparation for Thermodynamics 9 2.1 Variables of Thermodynamics 10 Extensive and Intensive Quantities 10 Units and Conversion Factors 10 2.2 Analytic Methods 10 Partial Differentiation 10 Exact Differentials 15 Homogeneous Functions 18 Exercises 21 References 27 3 The First Law of Thermodynamics 29 3.1 Definitions 29 Temperature 31 Work 33 3.2 The First Law of Thermodynamics 37 Energy 37 Heat 38 General Form of the First Law 38 Exercises 40 References 41 4 Enthalpy, Enthalpy of Reaction, and Heat Capacity 43 4.1 Enthalpy 44 Definition 44 Relationship between QV and QP 46 4.2 Enthalpy of Reactions 47 Definitions and Conventions 47 4.3 Enthalpy as a State Function 52 Enthalpy of Formation from Enthalpy of Reaction 52 Enthalpy of Formation from Enthalpy of Combustion 53 Enthalpy of Transition from Enthalpy of Combustion 53 Enthalpy of Conformational Transition of a Protein from Indirect Calorimetric Measurements 54 Enthalpy of Solid-State Reaction from Measurements of Enthalpy of Solution 56 4.4 Bond Enthalpies 57 Definition of Bond Enthalpies 57 Calculation of Bond Enthalpies 58 Enthalpy of Reaction from Bond Enthalpies 59 4.5 Heat Capacity 60 Definition 61 Some Relationships between CP and CV 62 Heat Capacities of Gases 64 Heat Capacities of Solids 67 Heat Capacities of Liquids 68 Other Sources of Heat Capacity Data 68 4.6 Enthalpy of Reaction as a Function of Temperature 68 Analytic Method 69 Arithmetic Method 71 Graphical or Numerical Methods 72 Exercises 72 References 78 5 Applications of the First Law to Gases 81 5.1 Ideal Gases 81 Definition 81 Enthalpy as a Function of Temperature Only 83 Relationship Between CP and CV 84 Calculation of the Thermodynamic Changes in Expansion Processes 84 5.2 Real Gases 94 Equations of State 94 Joule-Thomson Effect 98 Calculations of Thermodynamic Quantities in Reversible Expansions 102 Exercises 104 References 108 6 The Second Law of Thermodynamics 111 6.1 The Need for a Second Law 111 6.2 The Nature of the Second Law 112 Natural Tendencies Toward Equilibrium 112 Statement of the Second Law 112 Mathematical Counterpart of the Verbal Statement 113 6.3 The Carnot Cycle 113 The Forward Cycle 114 The Reverse Cycle 116 Alternative Statement of the Second Law 117 Carnot's Theorem 118 6.4 The Thermodynamic Temperature Scale 120 6.5 The Definition of S, the Entropy of a System 125 6.6 The Proof that S is a Thermodynamic Property 126 Any Substance in a Carnot Cycle 126 Any Substance in Any Reversible Cycle 127 Entropy S Depends Only on the State of the System 129 6.7 Entropy Changes in Reversible Processes 130 General Statement 130 Isothermal Reversible Changes 130 Adiabatic Reversible Changes 131 Reversible Phase Transitions 131 Isobaric Reversible Temperature Changes 132 Isochoric Reversible Temperature Changes 133 6.8 Entropy Changes in Irreversible Processes 133 Irreversible Isothermal Expansion of an Ideal Gas 133 Irreversible Adiabatic Expansion of an Ideal Gas 135 Irreversible Flow of Heat from a Higher Temperature to a Lower Temperature 136 Irreversible Phase Transitions 137 Irreversible Chemical Reactions 138 General Statement 139 6.9 General Equations for the Entropy of Gases 142 Entropy of the Ideal Gas 142 Entropy of a Real Gas 143 6.10 Temperature-Entropy Diagram 144 6.11 Entropy as an Index of Exhaustion 146 Exercises 150 References 157 7 Equilibrium and Spontaneity for Systems at Constant Temperature 159 7.1 Reversibility, Spontaneity, and Equilibrium 159 Systems at Constant Temperature and Volume 160 Systems at Constant Temperature and Pressure 162 Heat of Reaction as an Approximate Criterion of Spontaneity 164 7.2 Properties of the Gibbs, Helmholtz, and Planck Functions 165 The Functions as Thermodynamic Properties 165 Relationships among G, Y, and A 165 Changes in the Functions for Isothermal Conditions 165 Equations for Total Differentials 166 Pressure and Temperature Derivatives of the Functions 167 Equations Derived from the Reciprocity Relationship 169 7.3 The Gibbs Function and Chemical Reactions 170 Standard States 170 7.4 Pressure and Temperature Dependence of G 172 7.5 Useful Work and the Gibbs and Helmholtz Functions 175 Isothermal Changes 175 Changes at Constant Temperature and Pressure 177 Relationship between HP and QP When Useful Work is Performed 178 Application to Electrical Work 179 Gibbs-Helmholtz Equation 180 The Gibbs Function and Useful Work in Biologic Systems 181 Exercises 185 References 191 8 Application of the Gibbs Function and the Planck Function to Some Phase Changes 193 8.1 Two Phases at Equilibrium as a Function of Pressure and Temperature 193 Clapeyron Equation 194 Clausius-Clapeyron Equation 196 8.2 The Effect of an Inert Gas on Vapor Pressure 198 Variable Total Pressure at Constant Temperature 199 Variable Temperature at Constant Total Pressure 200 8.3 Temperature Dependence of Enthalpy of Phase Transition 200 8.4 Calculation of Change in the Gibbs Function for Spontaneous Phase Change 202 Arithmetic Method 202 Analytic Method 203 Exercises 205 References 210 9 Thermodynamics of Systems of Variable Composition 211 9.1 State Functions for Systems of Variable Composition 211 9.2 Criteria of Equilibrium and Spontaneity in Systems of Variable Composition 213 9.3 Relationships Among Partial Molar Properties of a Single Component 215 9.4 Relationships Between Partial Molar Quantities of Different Components 216 Partial Molar Quantities for Pure Phase 218 9.5 Escaping Tendency 219 Chemical Potential and Escaping Tendency 219 9.6 Chemical Equilibrium in Systems of Variable Composition 221 Exercises 223 Reference 226 10 Mixtures of Gases and Equilibrium in Gaseous Mixtures 227 10.1 Mixtures of Ideal Gases 227 The Entropy and Gibbs Function for Mixing Ideal Gases 228 The Chemical Potential of a Component of an Ideal Gas Mixture 230 Chemical Equilibrium in Ideal Gas Mixtures 231 Dependence of K on Temperature 232 Comparison of Temperature Dependence of G Degreesm and ln K 234 10.2 The Fugacity Function of a Pure Real Gas 236 Change of Fugacity with Pressure 237 Change of Fugacity with Temperature 238 10.3 Calculation of the Fugacity of a Real Gas 239 Graphical or Numerical Methods 240 Analytical Methods 244 10.4 Joule-Thomson Effect for a Van der Waals Gas 247 Approximate Value of a for a Van der Waals Gas 247 Fugacity at Low Pressures 248 Enthalpy of a Van der Waals Gas 248 Joule-Thomson Coefficient 249 10.5 Mixtures of Real Gases 249 Fugacity of a Component of a Gaseous Solution 250 Approximate Rule for Solutions of Real Gases 251 Fugacity Coefficients in Gaseous Solutions 251 Equilibrium Constant and Change in Gibbs Functions and Planck Functions for Reactions of Real Gases 252 Exercises 253 References 256 11 The Third Law of Thermodynamics 259 11.1 Need for the Third Law 259 11.2 Formulation of the Third Law 260 Nernst Heat Theorem 260 Planck's Formulation 261 Statement of Lewis and Randall 262 11.3 Thermodynamic Properties at Absolute Zero 263 Equivalence of G and H 263 CP in an Isothermal Chemical Reaction 263 Limiting Values of CP and CV 264 Temperature Derivatives of Pressure and Volume 264 11.4 Entropies at 298 K 265 Typical Calculations 266 Apparent Exceptions to the Third Law 270 Tabulations of Entropy Values 274 Exercises 277 References 280 12 Application of the Gibbs Function to Chemical Changes 281 12.1 Determination of G Degreesm from Equilibrium Measurements 281 12.2 Determination of G Degreesm from Measurements of Cell potentials 284 12.3 Calculation of G Degreesm from Calorimetric Measurements 285 12.4 Calculation of a Gibbs Function of a Reaction from Standard Gibbs Function of Formation 286 12.5 Calculation of a Standard Gibbs Function from Standard Entropies and Standard Enthalpies 287 Enthalpy Calculations 287 Entropy Calculations 290 Change in Standard Gibbs Function 290 Exercises 293 References 301 13 The Phase Rule 303 13.1 Derivation of the Phase Rule 303 Nonreacting Systems 304 Reacting Systems 306 13.2 One-Component Systems 307 13.3 Two-Component Systems 309 Two Phases at Different Pressures 312 Phase Rule Criterion of Purity 315 Exercises 316 References 316 14 The Ideal Solution 319 14.1 Definition 319 14.2 Some Consequences of the Definition 321 Volume Changes 321 Heat Effects 322 14.3 Thermodynamics of Transfer of a Component from One Ideal Solution to Another 323 14.4 Thermodynamics of Mixing 325 14.5 Equilibrium between a Pure Solid and an Ideal Liquid Solution 327 Change of Solubility with Pressure at a Fixed Temperature 328 Change of Solubility with Temperature 329 14.6 Equilibrium between an Ideal Solid Solution and an Ideal Liquid Solution 332 Composition of the Two Phases in Equilibrium 332 Temperature Dependence of the Equilibrium Compositions 333 Exercises 333 References 335 15 Dilute Solutions of Nonelectrolytes 337 15.1 Henry's Law 337 15.2 Nernst's Distribution Law 340 15.3 Raoult's Law 341 15.4 Van't Hoff's Law of Osmotic Pressure 344 Osmotic Work in Biological Systems 349 15.5 Van't Hoff's Law of Freezing-Point Depression and Boiling-Point Elevation 350 Exercises 353 References 355 16 Activities, Excess Gibbs Functions, and Standard States for Nonelectrolytes 357 16.1 Definitions of Activities and Activity Coefficients 358 Activity 358 Activity Coefficient 358 16.2 Choice of Standard States 359 Gases 359 Liquids and Solids 360 16.3 Gibbs Function and the Equilibrium Constant in Terms of Activity 365 16.4 Dependence of Activity on Pressure 367 16.5 Dependence of Activity on Temperature 368 Standard Partial Molar Enthalpies 368 Equation for Temperature Derivative of the Activity 369 16.6 Standard Entropy 370 16.7 Deviations from Ideality in Terms of Excess Thermodynamic Functions 373 Representation of G E m as a Function of Composition 374 16.8 Regular Solutions and Henry's Law 376 16.9 Regular Solutions and Limited Miscibility 378 Exercises 381 References 384 17 Determination of Nonelectrolyte Activities and Excess Gibbs Functions From Experimental Data 385 17.1 Activity from Measurements of Vapor Pressure 385 Solvent 385 Solute 386 17.2 Excess Gibbs Function from Measurement of Vapor Pressure 388 17.3 Activity of a Solute from Distribution between Two Immiscible Solvents 391 17.4 Activity from Measurement of Cell Potentials 393 17.5 Determination of the Activity of One Component from the Activity of the Other 397 Calculation of Activity of Solvent from That of Solute 398 Calculation of Activity of Solute from That of Solvent 399 17.6 Measurements of Freezing Points 400 Exercises 401 References 406 18 Calculation of Partial Molar Quantities and Excess Molar Quantities from Experimental Data: Volume and Enthalpy 407 18.1 Partial Molar Quantities by Differentiation of J as a Function of Composition 407 Partial Molar Volume 409 Partial Molar Enthalpy 413 Enthalpies of Mixing 414 Enthalpies of Dilution 417 18.2 Partial Molar Quantities of One Component from those of Another Component by Numerical Integration 420 Partial Molar Volume 421 Partial Molar Enthalpy 421 18.3 Analytic Methods for Calculation of Partial Molar Properties 422 Partial Molar Volume 422 Partial Molar Enthalpy 423 18.4 Changes in J for Some Processes in Solutions 423 Transfer Process 423 Integral Process 425 18.5 Excess Properties: Volume and Enthalpy 426 Excess Volume 426 Excess Enthalpy 426 Exercises 427 References 436 19 Activity, Activity Coefficients, and Osmotic Coefficients of Strong Electrolytes 439 19.1 Definitions and Standard states for Dissolved Electrolytes 440 Uni-univalent Electrolytes 440 Multivalent Electrolytes 443 Mixed Electrolytes 446 19.2 Determination of Activities of Strong Electrolytes 448 Measurement of Cell Potentials 449 Solubility Measurements 453 Colligative Property Measurement: The Osmotic Coefficient 455 Extension of Activity Coefficient Data to Additional Temperatures with Enthalpy of Dilution Data 460 19.3 Activity Coefficients of Some Strong Electrolytes 462 Experimental Values 462 Theoretical Correlation 462 Exercises 464 References 470 20 Changes in Gibbs Function for Processes in Solutions 471 20.1 Activity Coefficients of Weak Electrolytes 471 20.2 Determination of Equilibrium Constants for Dissociation of Weak Electrolytes 472 From Measurements of Cell Potentials 473 From Conductance Measurements 475 20.3 Some Typical Calculations for fG Degreesm 480 Standard Gibbs Function for Formation of Aqueous Solute: HCl 480 Standard Gibbs Function of Formation of Individual Ions: HCl 482 Standard Gibbs Function for Formation of Solid Solute in Aqueous Solution 482 Standard Gibbs Function for Formation of Ion of Weak Electrolyte 484 Standard Gibbs Function for Formation of Moderately Strong Electrolyte 485 Effect of Salt Concentration on Geological Equilibrium Involving Water 486 General Comments 486 20.4 Entropies of Ions 487 The Entropy of an Aqueous Solution of a Salt 488 Entropy of Formation of Individual Ions 488 Ion Entropies in Thermodynamic Calculations 491 Exercises 491 References 496 21 Systems Subject to a Gravitational or a Centrifugal Field 499 21.1 Dependence of the Gibbs Function on External Field 499 21.2 System in a Gravitational Field 502 21.3 System in a Centrifugal Field 505 Exercises 509 References 510 22 Estimation of Thermodynamic Quantities 511 22.1 Empirical Methods 511 Group Contribution Method of Andersen, Beyer, Watson, and Yoneda 512 Typical Examples of Estimating Entropies 516 Other Methods 522 Accuracy of the Approximate Methods 522 Equilibrium in Complex Systems 523 Exercises 523 References 524 23 Concluding Remarks 527 References 529 Appendix a Practical Mathematical Techniques 531 A.1 Analytical Methods 531 Linear Least Squares 531 Nonlinear Least Squares 534 A.2 Numerical and Graphical Methods 535 Numerical Differentiation 535 Numerical Integration 538 Use of the Digital Computer 540 Graphical Differentiation 541 Graphical Integration 542 Exercises 542 References 543 Index 545

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詳細情報

• NII書誌ID(NCID): BA87518985
• ISBN:
  • 9780471780151
• LCCN: 2008275257
• 出版国コード: us
• タイトル言語コード: eng
• 本文言語コード: eng
• 出版地: Hoboken
• ページ数/冊数: xxi, 563 p.
• 大きさ: 25 cm
• 分類:
  • LCC : QD504
• 件名:
  • LCSH : Thermodynamics