Chemical Thermodynamics : Basic Concepts and Methods

Content: Chapter 1 Introduction (pages 1–7): Chapter 2 Mathematical Preparation for Thermodynamics (pages 9–28): Chapter 3 The First Law of Thermodynamics (pages 29–41): Chapter 4 Enthalpy, Enthalpy of Reaction, and Heat Capacity (pages 43–79): Chapter 5 Applications of the First Law to Gases (pages 81–109): Chapter 6 The Second Law of Thermodynamics (pages 111–157): Chapter 7 Equilibrium and Spontaneity for Systems at Constant Temperature (pages 159–191): Chapter 8 Application of the Gibbs Function and the Planck Function to Some Phase Changes (pages 193–210): Chapter 9 Thermodynamics of Systems of Variable Composition (pages 211–226): Chapter 10 Mixtures of Gases and Equilibrium in Gaseous Mixtures (pages 227–257): Chapter 11 The Third Law of Thermodynamics (pages 259–280): Chapter 12 Application of the Gibbs Function to Chemical Changes (pages 281–301): Chapter 13 The Phase Rule (pages 303–317): Chapter 14 The Ideal Solution (pages 319–335): Chapter 15 Dilute Solutions of Nonelectrolytes (pages 337–355): Chapter 16 Activities, Excess Gibbs Functions, and Standard States for Nonelectrolytes (pages 357–384): Chapter 17 Determination of Nonelectrolyte Activities and Excess Gibbs Functions from Experimental Data (pages 385–406): Chapter 18 Calculation of Partial Molar Quantities and Excess Molar Quantities from Experimental Data: Volume and Enthalpy (pages 407–437): Chapter 19 Activity, Activity Coefficients, and Osmotic Coefficients of Strong Electrolytes (pages 439–470): Chapter 20 Changes in Gibbs Function for Processes in Solutions (pages 471–497): Chapter 21 Systems Subject to a Gravitational or a Centrifugal Field (pages 499–510): Chapter 22 Estimation of Thermodynamic Quantities (pages 511–525): Chapter 23 Concluding Remarks (pages 527–530): Cover Page......Page 1 Title Page......Page 0 ISBN 0471780154......Page 3 CONTENTS (with page links)......Page 5 PREFACE......Page 17 1.1 Origins of Chemical Thermodynamics......Page 21 1.3 Limitations of Classic Thermodynamics......Page 24 References......Page 26 2 MATHEMATICAL PREPARATION FOR THERMODYNAMICS......Page 29 Partial Differentiation......Page 30 Exact Differentials......Page 35 Homogeneous Functions......Page 38 Exercises......Page 41 References......Page 47 3.1 Definitions......Page 49 Temperature......Page 51 Work......Page 53 Energy......Page 57 General Form of the First Law......Page 58 Exercises......Page 60 References......Page 61 4 ENTHALPY, ENTHALPY OF REACTION, AND HEAT CAPACITY......Page 63 Definition......Page 64 Relationship between Q(V) and Q(P)......Page 66 Definitions and Conventions......Page 67 Enthalpy of Formation from Enthalpy of Reaction......Page 72 Enthalpy of Transition from Enthalpy of Combustion......Page 73 Enthalpy of Conformational Transition of a Protein from Indirect Calorimetric Measurements......Page 74 Enthalpy of Solid-State Reaction from Measurements of Enthalpy of Solution......Page 76 Definition of Bond Enthalpies......Page 77 Calculation of Bond Enthalpies......Page 78 Enthalpy of Reaction from Bond Enthalpies......Page 79 4.5 Heat Capacity......Page 80 Definition......Page 81 Some Relationships between C(P) and C(V)......Page 82 Heat Capacities of Gases......Page 84 Heat Capacities of Solids......Page 87 4.6 Enthalpy of Reaction as a Function of Temperature......Page 88 Analytic Method......Page 89 Arithmetic Method......Page 91 Exercises......Page 92 References......Page 98 Definition......Page 101 Enthalpy as a Function of Temperature Only......Page 103 Calculation of the Thermodynamic Changes in Expansion Processes......Page 104 Equations of State......Page 114 Joule-Thomson Effect......Page 118 Calculations of Thermodynamic Quantities in Reversible Expansions......Page 122 Exercises......Page 124 References......Page 128 6.1 The Need for a Second Law......Page 131 Statement of the Second Law......Page 132 6.3 The Carnot Cycle......Page 133 The Forward Cycle......Page 134 The Reverse Cycle......Page 136 Alternative Statement of the Second Law......Page 137 Carnot’s Theorem......Page 138 6.4 The Thermodynamic Temperature Scale......Page 140 6.5 The Definition of S, the Entropy of a System......Page 145 Any Substance in a Carnot Cycle......Page 146 Any Substance in Any Reversible Cycle......Page 147 Entropy S Depends Only on the State of the System......Page 149 Isothermal Reversible Changes......Page 150 Reversible Phase Transitions......Page 151 Isobaric Reversible Temperature Changes......Page 152 Irreversible Isothermal Expansion of an Ideal Gas......Page 153 Irreversible Adiabatic Expansion of an Ideal Gas......Page 155 Irreversible Flow of Heat from a Higher Temperature to a Lower Temperature......Page 156 Irreversible Phase Transitions......Page 157 Irreversible Chemical Reactions......Page 158 General Statement......Page 159 Entropy of the Ideal Gas......Page 162 Entropy of a Real Gas......Page 163 6.10 Temperature-Entropy Diagram......Page 164 6.11 Entropy as an Index of Exhaustion......Page 166 Exercises......Page 170 References......Page 177 7.1 Reversibility, Spontaneity, and Equilibrium......Page 179 Systems at Constant Temperature and Volume......Page 180 Systems at Constant Temperature and Pressure......Page 182 Heat of Reaction as an Approximate Criterion of Spontaneity......Page 184 Changes in the Functions for Isothermal Conditions......Page 185 Equations for Total Differentials......Page 186 Pressure and Temperature Derivatives of the Functions......Page 187 Equations Derived from the Reciprocity Relationship......Page 189 Standard States......Page 190 Isothermal Changes......Page 195 Changes at Constant Temperature and Pressure......Page 197 Relationship between ΔH(P) and Q(P) When Useful Work is Performed......Page 198 Application to Electrical Work......Page 199 Gibbs-Helmholtz Equation......Page 200 The Gibbs Function and Useful Work in Biologic Systems......Page 201 Exercises......Page 205 References......Page 211 8.1 Two Phases at Equilibrium as a Function of Pressure and Temperature......Page 213 Clapeyron Equation......Page 214 Clausius-Clapeyron Equation......Page 216 8.2 The Effect of an Inert Gas on Vapor Pressure......Page 218 Variable Total Pressure at Constant Temperature......Page 219 8.3 Temperature Dependence of Enthalpy of Phase Transition......Page 220 Arithmetic Method......Page 222 Analytic Method......Page 223 Exercises......Page 225 References......Page 230 9.1 State Functions for Systems of Variable Composition......Page 231 9.2 Criteria of Equilibrium and Spontaneity in Systems of Variable Composition......Page 233 9.3 Relationships Among Partial Molar Properties of a Single Component......Page 235 9.4 Relationships Between Partial Molar Quantities of Different Components......Page 236 Partial Molar Quantities for Pure Phase......Page 238 Chemical Potential and Escaping Tendency......Page 239 9.6 Chemical Equilibrium in Systems of Variable Composition......Page 241 Exercises......Page 243 Reference......Page 246 10.1 Mixtures of Ideal Gases......Page 247 The Entropy and Gibbs Function for Mixing Ideal Gases......Page 248 The Chemical Potential of a Component of an Ideal Gas Mixture......Page 250 Chemical Equilibrium in Ideal Gas Mixtures......Page 251 Dependence of K on Temperature......Page 252 10.2 The Fugacity Function of a Pure Real Gas......Page 256 Change of Fugacity with Pressure......Page 257 Change of Fugacity with Temperature......Page 258 10.3 Calculation of the Fugacity of a Real Gas......Page 259 Graphical or Numerical Methods......Page 260 Analytical Methods......Page 264 Approximate Value of α for a Van der Waals Gas......Page 267 Enthalpy of a Van der Waals Gas......Page 268 10.5 Mixtures of Real Gases......Page 269 Fugacity of a Component of a Gaseous Solution......Page 270 Fugacity Coefficients in Gaseous Solutions......Page 271 Equilibrium Constant and Change in Gibbs Functions and Planck Functions for Reactions of Real Gases......Page 272 Exercises......Page 273 References......Page 276 11.1 Need for the Third Law......Page 279 Nernst Heat Theorem......Page 280 Planck’s Formulation......Page 281 Statement of Lewis and Randall......Page 282 ΔC(P) in an Isothermal Chemical Reaction......Page 283 Temperature Derivatives of Pressure and Volume......Page 284 11.4 Entropies at 298 K......Page 285 Typical Calculations......Page 286 Apparent Exceptions to the Third Law......Page 290 Tabulations of Entropy Values......Page 294 Exercises......Page 297 References......Page 300 12.1 Determination of ΔG°(m) from Equilibrium Measurements......Page 301 12.2 Determination of ΔG°(m) from Measurements of Cell potentials......Page 304 12.3 Calculation of ΔG°(m) from Calorimetric Measurements......Page 305 12.4 Calculation of a Gibbs Function of a Reaction from Standard Gibbs Function of Formation......Page 306 Enthalpy Calculations......Page 307 Change in Standard Gibbs Function......Page 310 Exercises......Page 313 References......Page 321 13.1 Derivation of the Phase Rule......Page 323 Nonreacting Systems......Page 324 Reacting Systems......Page 326 13.2 One-Component Systems......Page 327 13.3 Two-Component Systems......Page 329 Two Phases at Different Pressures......Page 332 Phase Rule Criterion of Purity......Page 335 References......Page 336 14.1 Definition......Page 339 Volume Changes......Page 341 Heat Effects......Page 342 14.3 Thermodynamics of Transfer of a Component from One Ideal Solution to Another......Page 343 14.4 Thermodynamics of Mixing......Page 345 14.5 Equilibrium between a Pure Solid and an Ideal Liquid Solution......Page 347 Change of Solubility with Pressure at a Fixed Temperature......Page 348 Change of Solubility with Temperature......Page 349 Composition of the Two Phases in Equilibrium......Page 352 Exercises......Page 353 References......Page 355 15.1 Henry’s Law......Page 357 15.2 Nernst’s Distribution Law......Page 360 15.3 Raoult’s Law......Page 361 15.4 Van’t Hoff’s Law of Osmotic Pressure......Page 364 Osmotic Work in Biological Systems......Page 369 15.5 Van’t Hoff’s Law of Freezing-Point Depression and Boiling-Point Elevation......Page 370 Exercises......Page 373 References......Page 375 16 ACTIVITIES, EXCESS GIBBS FUNCTIONS, AND STANDARD STATES FOR NONELECTROLYTES......Page 377 Activity Coefficient......Page 378 Gases......Page 379 Liquids and Solids......Page 380 16.3 Gibbs Function and the Equilibrium Constant in Terms of Activity......Page 385 16.4 Dependence of Activity on Pressure......Page 387 Standard Partial Molar Enthalpies......Page 388 Equation for Temperature Derivative of the Activity......Page 389 16.6 Standard Entropy......Page 390 16.7 Deviations from Ideality in Terms of Excess Thermodynamic Functions......Page 393 Representation of G(E)(m) as a Function of Composition......Page 394 16.8 Regular Solutions and Henry’s Law......Page 396 16.9 Regular Solutions and Limited Miscibility......Page 398 Exercises......Page 401 References......Page 404 Solvent......Page 405 Solute......Page 406 17.2 Excess Gibbs Function from Measurement of Vapor Pressure......Page 408 17.3 Activity of a Solute from Distribution between Two Immiscible Solvents......Page 411 17.4 Activity from Measurement of Cell Potentials......Page 413 17.5 Determination of the Activity of One Component from the Activity of the Other......Page 417 Calculation of Activity of Solvent from That of Solute......Page 418 Calculation of Activity of Solute from That of Solvent......Page 419 17.6 Measurements of Freezing Points......Page 420 Exercises......Page 421 References......Page 426 18.1 Partial Molar Quantities by Differentiation of J as a Function of Composition......Page 427 Partial Molar Volume......Page 429 Partial Molar Enthalpy......Page 433 Enthalpies of Mixing......Page 434 Enthalpies of Dilution......Page 437 18.2 Partial Molar Quantities of One Component from those of Another Component by Numerical Integration......Page 440 Partial Molar Enthalpy......Page 441 Partial Molar Volume......Page 442 Transfer Process......Page 443 Integral Process......Page 445 Excess Enthalpy......Page 446 Exercises......Page 447 References......Page 456 19 ACTIVITY, ACTIVITY COEFFICIENTS, AND OSMOTIC COEFFICIENTS OF STRONG ELECTROLYTES......Page 459 Uni-univalent Electrolytes......Page 460 Multivalent Electrolytes......Page 463 Mixed Electrolytes......Page 466 19.2 Determination of Activities of Strong Electrolytes......Page 468 Measurement of Cell Potentials......Page 469 Solubility Measurements......Page 473 Colligative Property Measurement: The Osmotic Coefficient......Page 475 Extension of Activity Coefficient Data to Additional Temperatures with Enthalpy of Dilution Data......Page 480 Theoretical Correlation......Page 482 Exercises......Page 484 References......Page 490 20.1 Activity Coefficients of Weak Electrolytes......Page 491 20.2 Determination of Equilibrium Constants for Dissociation of Weak Electrolytes......Page 492 From Measurements of Cell Potentials......Page 493 From Conductance Measurements......Page 495 Standard Gibbs Function for Formation of Aqueous Solute: HCl......Page 500 Standard Gibbs Function for Formation of Solid Solute in Aqueous Solution......Page 502 Standard Gibbs Function for Formation of Ion of Weak Electrolyte......Page 504 Standard Gibbs Function for Formation of Moderately Strong Electrolyte......Page 505 General Comments......Page 506 20.4 Entropies of Ions......Page 507 Entropy of Formation of Individual Ions......Page 508 Exercises......Page 511 References......Page 516 21.1 Dependence of the Gibbs Function on External Field......Page 519 21.2 System in a Gravitational Field......Page 522 21.3 System in a Centrifugal Field......Page 525 Exercises......Page 529 References......Page 530 22.1 Empirical Methods......Page 531 Group Contribution Method of Andersen, Beyer, Watson, and Yoneda......Page 532 Typical Examples of Estimating Entropies......Page 536 Accuracy of the Approximate Methods......Page 542 Exercises......Page 543 References......Page 544 23 CONCLUDING REMARKS......Page 547 References......Page 549 Linear Least Squares......Page 551 Nonlinear Least Squares......Page 554 Numerical Differentiation......Page 555 Numerical Integration......Page 558 Use of the Digital Computer......Page 560 Graphical Differentiation......Page 561 Exercises......Page 562 References......Page 563 INDEX (with page links)......Page 565 "For more than fifty years, this critically acclaimed and highly influential publication has been the textbook of choice in the field of chemical thermodynamics. This Seventh Edition not only brings the text thoroughly up to date with the latest developments and applications, it also offers new features that better enable students to master key concepts and apply them in practice." "While thoroughly revised and updated, the text's fundamental objectives remain unchanged: to present the foundations and interrelationships of thermodynamics and to enable students to apply basic concepts in solving problems typically encountered by chemists, biologists, geologists, and materials scientists. Moreover, the text continues to maintain a logical unity throughout by focusing on the laws of classical thermodynamics and applications to gases, solutions, phase equilibria, and chemical equilibria."--BOOK JACKET.

• 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.