Chemical Thermodynamics: Basic Theory and Methods, 6th Edition

by Irwing M. Klotz (Emeritus, Northwestern Univ.); Robert M. Rosenberg (Emeritus, Lawrence Univ., and Visiting Professor Northwestern Univ.)

Edition: 6th

ISBN13: 9780471331070

ISBN10: 0471331074

Format: Hardcover

Pub. Date: 2000-03-01

Publisher(s): Wiley-Interscience

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Summary

"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.

Author Biography

<B>IRVING M. KLOTZ, PhD</b>, is Morrison Professor Emeritus, Northwestern University, Evanston, Illinois. <p> gt;ROBERT M. ROSENBERG, PhD</b>, is currently a visiting professor of chemistry at Northwestern University.

Preface

xix

Introduction

(7)

Origins of Chemical Thermodynamics

(3)

Objectives of Chemical Thermodynamics

(1)

Limitations of Classical Thermodynamics

(4)

References

(2)

Mathematical Preparation for Thermodynamics

(20)

Variables of Thermodynamics

(1)

Extensive and Intensive Quantities

(1)

Units and Conversion Factors

(1)

Theoretical Methods

(19)

Partial Differentiation

(1)

Equation for the Total Differential

(3)

Conversion Formulas

(2)

Exact Differentials

(1)

Example of the Gravitational Field

(1)

General Formulation

(1)

Reciprocity Characteristic

(1)

Homogeneous Functions

(1)

Definition

(1)

Euler's Theorem

(8)

References

(2)

The First Law of Thermodynamics

(14)

Definitions

(9)

Temperature

(2)

Work

(5)

The First Law of Thermodynamics

(5)

Energy

(1)

Heat

(1)

General Form of the First Law

(2)

Exercises

(1)

References

(2)

Enthalpy, Enthalpy of Reaction, and Heat Capacity

(36)

Enthalpy

(3)

Definition

(1)

Relationship between QV and QP

(2)

Enthalpy of Reactions

(4)

Definitions and Conventions

(1)

Some Standard States

(1)

Enthalpy of Formation

(3)

Additivity of Enthalpies of Reaction

(5)

Enthalpy of Formation from Enthalpy of Reaction

(1)

Enthalpy of Formation from Enthalpy of Combustion

(1)

Enthalpy of Transition from Enthalpy of Combustion

(1)

Enthalpy of Conformational Transition of a Protein from Indirect Calorimetric Measurements

(2)

Enthalpy of Solid State Reaction from Measurements of Enthalpy of Solution

(1)

Bond Enthalpies

(4)

Definition of Bond Enthalpies

(1)

Calculation of Bond Enthalpies

(1)

Enthalpy of Reaction from Bond Enthalpies

(2)

Heat Capacity

(8)

Definition

(1)

Fundamental Statement

(1)

Derived Relationships

(1)

Some Relationships between CP and CV

(3)

Heat Capacities of Gases

(1)

Heat Capacities of Solids

(3)

Heat Capacities of Liquids

(1)

Sources of Heat Capacity Data

(1)

Enthalpy of Reaction as a Function of Temperature

(11)

Analytic Method

(2)

Arithmetic Method

(1)

Graphical or Numerical Methods

(1)

Exercises

(5)

References

(2)

Application of the first Law to Gases

(29)

Ideal Gases

(13)

Definition

(2)

Enthalpy a Function of Temperature Only

(1)

Relationship between CP and CV

(1)

Calculation of the Thermodynamic Changes in Expansion Processes

(1)

Isothermal

(6)

Adiabatic

(4)

Real Gases

(16)

Semiempirical Equations

(3)

Virial Function

(1)

Joule-Thomson Effect

(1)

Isenthalpic Nature

(2)

Joule-Thomson Coefficient

(2)

Joule-Thomson Inversion Temperature

(1)

Calculation of Thermodynamic Quantities in Reversible Expansions

100

(1)

Isothermal

100

(1)

Adiabatic

101

(1)

Exercises

102

(3)

References

105

(2)

The Second Law of Thermodynamics

107

(47)

The Need for a Second Law

107

(1)

The Nature of the Second Law

108

(1)

Natural Tendencies Toward Equilibrium

108

(1)

Statement of the Second Law

108

(1)

Mathematical Counterpart of the Verbal Statement

109

(1)

The Carnot Cycle

109

(7)

The Forward Cycle

110

(2)

The Reverse Cycle

112

(1)

Alternative Statement of the Second Law

113

(1)

Carnot's Theorem

113

(3)

The Thermodynamic Temperature Scale

116

(5)

The Definition of S, The Entropy of a System

121

(1)

The Proof that S Is a Thermodynamic Property

122

(4)

Any Substance in a Carnot Cycle

122

(1)

Any Substance in Any Reversible Cycle

123

(2)

Entropy S Depends Only on the State of the System

125

(1)

Entropy Changes in Reversible Processes

126

(3)

General Statement

126

(1)

Isothermal Reversible Changes

126

(1)

Adiabatic Reversible Changes

127

(1)

Reversible Phase Transitions

127

(1)

Isobaric Reversible Temperature Change

128

(1)

Isochoric Reversible Temperature Change

128

(1)

Entropy Changes in Irreversible Processes

129

(9)

Irreversible Isothermal Expansion of an Ideal Gas

129

(2)

Irreversible Adiabatic Expansion of an Ideal Gas

131

(1)

Irreversible Flow of Heat from a Higher to a Lower Temperature

132

(1)

Irreversible Phase Transition

133

(2)

Irreversible Chemical Reaction

135

(1)

General Statement

135

(3)

General Equations for the Entropy of Gases

138

(3)

Entropy of an Ideal Gas

138

(1)

Entropy of a Real Gas

139

(2)

Temperature-Entropy Diagram

141

(1)

Entropy as an Index of Exhaustion

142

(12)

Exercises

146

(6)

References

152

(2)

Equilibrium and Spontaneity for Systems at Constant Temperature: The Gibbs, Helmholtz, Planck, and Massieu Functions

154

(43)

Reversibility, Spontaneity, and Equilibrium

154

(6)

Systems at Constant Temperature and Volume

155

(2)

Systems at Constant Temperature and Pressure

157

(2)

Heat of Reaction as an Approximate Criterion of Spontaneity

159

(1)

Properties of the Gibbs, Helmholtz, and Planck Functions

160

(5)

The Functions as Thermodynamic Properties

160

(1)

Relationships among G, Y, and A

160

(1)

Changes in the Functions for Isothermal Conditions

160

(1)

Equations for Total Differentials

161

(1)

Pressure and Temperature Coefficients of the Functions

162

(2)

Equations Derived from the Reciprocity Relationship

164

(1)

The Planck Function and the Equilibrium Constant

165

(13)

Standard States

165

(1)

Relationship between ΔYom and the Equilibrium Constant for Gaseous Reactions

166

(6)

Dependence of K on Temperature

172

(1)

Pressure and Temperature Dependence of ΔG

173

(1)

Temperature Dependence

174

(1)

Pressure Dependence

175

(1)

General Expression

175

(1)

Comparison of Temperature Dependence of ΔGom and ln K

176

(2)

Useful Work and the Gibbs and Helmholtz Functions

178

(19)

Isothermal Changes

178

(3)

Changes at Constant Temperature and Pressure

181

(1)

Relationship between δHP and QP When Useful Work Is Done

182

(1)

Application to Electrical Work

182

(2)

Gibbs-Helmholtz Equation

184

(1)

The Gibbs Function and Useful Work in Biological Systems

185

(1)

Biosynthetic Work

185

(4)

Mechanical Work

189

(1)

Osmotic Work

189

(1)

Exercises

189

(7)

References

196

(1)

Application of the Gibbs Function and the Planck Function to some Phase Changes

197

(19)

Two Phases at Equilibrium as a Function of Pressure and Temperature

197

(5)

Clapeyron Equation

198

(2)

Clausius-Clapeyron Equation

200

(2)

The Effect of an Inert Gas on Vapor Pressure

202

(2)

Variable Total Pressure at Constant Temperature

203

(1)

Variable Temperature at Constant Total Pressure

204

(1)

Temperature Dependence of Enthalpy of Phase Transition

204

(2)

Calculation of Change in the Gibbs Function and Change in the Planck Function for Spontaneous Phase Change

206

(10)

Arithmetic Method

207

(1)

Analytic Method

207

(2)

Exercises

209

(6)

References

215

(1)

The Third Law of Thermodynamics

216

(23)

Need for the Third Law

216

(1)

Formulation of the Third Law

217

(3)

Nernst Heat Theorem

218

(1)

Planck's Formulation

218

(1)

Statement of Lewis and Randall

219

(1)

Thermodynamic Properties at Absolute Zero

220

(3)

Equivalence of G and H

220

(1)

ΔCP in an Isothermal Chemical Transformation

220

(1)

Limiting Values of CP and CV

221

(1)

Temperature Coefficients of Pressure and Volume

222

(1)

Entropies at 298 K

223

(16)

Typical Calculations

223

(1)

For Solid or Liquid

223

(3)

For a Gas

226

(1)

Apparent Exceptions to the Third Law

227

(4)

Tabulation of Entropy Values

231

Exercises

205

(32)

References

237

(2)

Application of the Gibbs Function and the Planck Function to Chemical Changes

239

(23)

Determination of Gibbs Function and Planck Function from Equilibrium Measurements

239

(3)

Determination of Gibbs Function and Planck Function from Measurements of Cell Potentials

242

(1)

Calculation of Gibbs Function and Planck Function from Calorimetric Measurements

243

(2)

Calculation of Gibbs Function and Planck Function of Reaction from Standard Gibbs Function and Standard Planck Function of Formation

245

(1)

Calculation of Standard Gibbs Function and Standard Planck Function from Standard Entropies and Standard Enthalpies

245

(17)

Enthalpy Calculations

245

(2)

Entropy Calculations

247

(2)

Change in Standard Gibbs Function and Standard Planck Function

249

(3)

Exercises

252

(8)

References

260

(2)

Thermodynamics of Systems of Variable Composition

262

(17)

State Functions for Systems of Variable Composition

262

(2)

Criteria of Equilibrium and Spontaneity in Systems of Variable Composition

264

(2)

Relationships among Partial Molar Properties of a Single Component

266

(1)

Relationships between Partial Molar Quantities of Different Components

267

(3)

Partial Molar Quantities for Pure Phase

269

(1)

Escaping Tendency

270

(2)

Chemical Potential and Escaping Tendency

270

(2)

Chemical Equilibrium in Systems of Variable Composition

272

(7)

Exercises

275

(3)

Reference

278

(1)

Mixtures of Gases

279

(28)

Mixtures of Ideal Gases

279

(5)

The Entropy and Gibbs Function for Mixing Ideal Gases

280

(1)

The Chemical Potential of a Component of an Ideal Gas Mixture

281

(2)

Chemical Equilibrium in Ideal Gas Mixtures

283

(1)

The Fugacity Function of a Pure Real Gas

284

(4)

Change of Fugacity with Pressure

285

(1)

Change of Fugacity with Temperature

286

(2)

Calculation of the Fugacity of a Real Gas

288

(8)

Graphical or Numerical Methods

288

(1)

Using the α Function

288

(2)

Using the Compressibility Factor

290

(1)

Analytical Methods

291

(1)

Based on the Virial Equation

291

(2)

Based on the Redlich-Kwong Equation of State

293

(2)

An Approximate Method

295

(1)

Joule-Thomson Effect for a van der Waals Gas

296

(3)

Approximate Value of α for a van der Waals Gas

296

(1)

Fugacity at Low Pressures

297

(1)

Enthalpy of a van der Waals Gas

298

(1)

Joule-Thomson Coefficient

298

(1)

Mixtures of Real Gases

299

(8)

Fugacity of a Component of a Gaseous Solution

299

(1)

Approximate Rule for Solutions of Real Gases

300

(1)

Fugacity Coefficients in Gaseous Solution

301

(1)

Equilibrium Constant and Change in Gibbs Function and Planck Function for Reactions Involving Real Gases

301

(1)

Exercises

302

(3)

References

305

(2)

The Phase Rule

307

(15)

Derivation of the Phase Rule

307

(4)

Nonreacting Systems

307

(1)

Mechanical Equilibrium

308

(1)

Thermal Equilibrium

308

(1)

Transfer Equilibrium

309

(1)

The Phase Rule

310

(1)

Reacting Systems

310

(1)

One-Component Systems

311

(2)

Two-Component Systems

313

(9)

Two Phases at Different Pressures

316

(3)

Phase Rule Criterion of Purity

319

(1)

Exercises

319

(1)

References

320

(2)

The Ideal Solution

322

(18)

Definition

322

(2)

Some Consequences of the Definition

324

(2)

Volume Changes

324

(1)

Heat Effects

325

(1)

Thermodynamics of Transfer of a Component from One Ideal Solution to Another

326

(2)

Thermodynamics of Mixing

328

(2)

Equilibrium between a Pure Solid and an Ideal Liquid Solution

330

(6)

Change of Solubility with Pressure at a Fixed Temperature

332

(1)

Change of Solubility with Temperature

332

(4)

Equilibrium between an Ideal Solid Solution and an Ideal Liquid Solution

336

(4)

Composition of the Two Phases in Equilibrium

336

(1)

Temperature Dependence of the Equilibrium Compositions

337

(1)

Exercises

338

(1)

References

339

(1)

Dilute Solutions of Nonelectrolyte

340

(19)

Henry's Law

340

(3)

Nernst's Distribution Law

343

(1)

Raoult's Law

344

(3)

van't Hoff's Law of Osmotic Pressure

347

(6)

Osmotic Work in Biological Systems

352

(1)

van't Hoff's Law of Freezing Point Depression and Boiling Point Elevation

353

(6)

Exercises

356

(2)

References

358

(1)

Activities, Excess Gibbs Function, and Standard States for Nonelectrolytes

359

(25)

Definitions of Activities and Activity Coefficients

360

(1)

Activity

360

(1)

Activity Coefficient

360

(1)

Choice of Standard States

361

(6)

Gases

361

(1)

Liquids and Solids

362

(1)

Pure Substances

362

(1)

Solvent in Solution

362

(2)

Solute in Solution

364

(3)

Gibbs Function and the Equilibrium Constant in Terms of Activity

367

(2)

Dependence of Activity on Pressure

369

(1)

Dependence of Activity on Temperature

370

(3)

Standard Partial Molar Enthalpies

370

(1)

Solvent

370

(1)

Solute

370

(1)

Equation for Temperature Coefficient of the Activity

371

(2)

Standard Entropy

373

(2)

Deviations from Ideality in Terms of Excess Thermodynamic Quantities

375

(9)

Representation of Excess Gibbs Function as a Function of Composition

378

(2)

Exercises

380

(3)

References

383

(1)

Determination of Nonelectrolyte Activities and Excess Gibbs Function from Experimental Data

384

(23)

Activity from Measurements of Vapor Pressure

384

(3)

Solvent

384

(1)

Solute

385

(2)

Excess Gibbs Function from Measurement of Vapor Pressure

387

(1)

Activity of a Solute from Distribution of Solute between Two Immiscible Solvents

388

(5)

Activity from Measurements of Cell Potentials

393

(4)

Determination of the Activity of One Component from Known Values of the Activity of the Other

397

(3)

Calculation of Activity of Solvent from That of Solute

397

(1)

Calculation of Activity of Solute from That of Solvent

398

(2)

Measurements of Freezing Points

400

(7)

Exercises

400

(5)

References

405

(2)

Calculation of Partial Molar Quantities and Excess Molar Quantities from Experimental Data: Volume and Enthalpy

407

(31)

Partial Molar Quantities by Defferentiation of J as a Function of Composition

407

(13)

Partial Molar Volumes

409

(4)

Partial Molar Enthalpies

413

(1)

Enthalpies of Mixing

413

(4)

Enthalpies of Dilution

417

(3)

Partial Molar Quantities of One Component from those of Another Component by Numerical Integration

420

(2)

Partial Molar Volumes

421

(1)

Partial Molar Enthalpies

422

(1)

Analytic Methods for Partial Molar Properties

422

(2)

Partial Molar Volumes

422

(1)

Partial Molar Enthalpies

423

(1)

Changes in J for Some Processes Involving Solutions

424

(3)

Differential Process

424

(2)

Integral Process

426

(1)

Excess Properties: Volume and Enthalpy

427

(11)

Excess Volume

427

(1)

Excess Enthalpy

428

(1)

Exercises

428

(8)

References

436

(2)

Activity, Activity Coefficients, and Osmotic Coefficients of Strong Electrolytes

438

(34)

Definitions and Standard States for Dissolved Electrolytes

438

(10)

Uni-univalent Electrolytes

438

(4)

Multivalent Electrolytes

442

(1)

Symmetrical Salts

442

(1)

Unsymmetrical Salts

442

(3)

General Case

445

(1)

Mixed Electrolytes

446

(2)

Determination of Activities of Strong Electrolytes

448

(14)

Measurement of Cell Potentials

448

(5)

Solubility Measurements

453

(1)

Colligative Property Measurement: the Osmotic Coefficient

454

(5)

Extension of Activity Coefficient Data to Additional Temperatures with Enthalpy of Dilution Data

459

(3)

Activity Coefficients of Some Strong Electrolytes

462

(10)

Experimental Values

462

(1)

Theoretical Correlation

462

(3)

Exercises

465

(5)

References

470

(2)

Changes in Gibbs Function for Processes Involving Solutions

472

(28)

Activity Coefficients of Weak Electrolytes

472

(1)

Determination of Equilibrium Constants for Dissociation of Weak Electrolytes

473

(9)

From Measurements of Cell Potentials

474

(2)

From Conductance Measurements

476

(6)

Some Typical Calculations for Gibbs Function of Formation

482

(8)

Standard Gibbs Function for Formation of Aqueous Solute: HCl

482

(1)

Standard Gibbs Function for Formation of Individual Ions: HCl

483

(1)

Standard Gibbs Function for Formation of Solid Solute in Aqueous Solution

484

(1)

Solute Very Soluble: Sodium Chloride

484

(1)

Slightly Soluble Solute: Silver Chloride

485

(1)

Standard Gibbs Function for Formation of Ion of Weak Electrolyte

486

(1)

Standard Gibbs Function for Formation of Moderately Strong Electrolyte

487

(1)

Effect of Salt Concentration on Geological Equilibrium Involving Water

488

(1)

General Comments

489

(1)

Entropies of Ions

490

(10)

The Entropy of an Aqueous Solution of a Salt

490

(1)

Calculation of Entropy of Formation of Individual Ions

491

(1)

Utilization of Ion Entropies in Thermodynamic Calculations

492

(1)

Exercises

493

(6)

References

499

(1)

Systems Subject to a Gravitational Field

500

(12)

Dependence of the Gibbs Function on Field

502

(1)

System in a Gravitational Field

502

(3)

System in a Centrifugal Field

505

(7)

Exercises

510

(1)

References

511

(1)

Estimation of Thermodynamic Quantities

512

(14)

Empirical Methods

512

(14)

Group Contribution Method of Andersen, Beyer, Watson, and Yoneda

513

(4)

Typical Problems in Estimating Entropies

517

(1)

Other Methods

518

(5)

Accuracy of the Approximate Methods

523

(1)

Equilibrium in Complex Systems

523

(1)

Exercises

523

(1)

References

524

(2)

Practical Mathematical Techniques

526

(14)

Analytical Methods

526

(5)

Linear Least Squares

526

(4)

Nonlinear Least Squares

530

(1)

Numerical and Graphical Methods

531

(9)

Numerical Differentiation

531

(2)

Numerical Integration

533

(2)

Use of the Digital Computer

535

(1)

Graphical Differentiation

536

(2)

Graphical Integration

538

(1)

Exercises

538

(1)

References

538

(2)

Concluding Remarks

540

(4)

References

542

(2)

Index

544

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Chemical Thermodynamics: Basic Theory and Methods, 6th Edition

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