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Preface xv
Introduction 1 (8)
Nature of Physical Chemistry 1 (2)
Units 3 (3)
Force 4 (1)
Pressure 4 (2)
Energy 6 (1)
Atomic Mass, Molecular Mass, and the 6 (3)
Chemical Mole
The Gas Laws 9 (28)
Some Basic Definitions 9 (1)
An Operational Definition of Temperature 10 (1)
Boyle's Law 11 (1)
Charles' and Gay--Lussac's Law 11 (2)
Avogadro's Law 13 (1)
The Ideal Gas Equation 14 (2)
Dalton's Law of Partial Pressures 16 (2)
Real Gases 18 (6)
The van der Waals Equation 19 (3)
The Virial Equation of State 22 (2)
Condensation of Gases and the Critical State 24 (6)
Problems 30 (7)
Kinetic Theory of Gases 37 (38)
The Model 37 (1)
Pressure of a Gas 38 (2)
Kinetic Energy and Temperature 40 (1)
The Maxwell Distribution Laws 41 (6)
Molecular Collisions and the Mean Free Path 47 (4)
Gas Viscosity 51 (3)
Graham's Laws of Diffusion and Effusion 54 (3)
Equipartition of Energy 57 (7)
Derivation of Equation 3.24 64 (2)
Total and Partial Differentiation 66 (3)
Problems 69 (6)
The First Law of Thermodynamics 75 (50)
Work and Heat 75 (7)
Work 75 (6)
Heat 81 (1)
The First Law of Thermodynamics 82 (3)
Enthalpy 85 (5)
A Closer Look at Heat Capacities 90 (3)
Gas Expansion 93 (5)
Isothermal Expansion 93 (1)
Adiabatic Expansion 94 (4)
Thermochemistry 98 (8)
Standard Enthalpy of Formation 98 (6)
Dependence of Enthalpy of Reaction on 104 (2)
Temperature
Bond Energies and Bond Enthalpies 106 (7)
Bond Enthalpy and Bond Dissociation 108 (5)
Enthalpy
Exact and Inexact Differentials 113 (4)
Problems 117 (8)
The Second Law of Thermodynamics 125 (40)
Spontaneous Process 125 (2)
Entropy 127 (4)
Statistical Definition of Entropy 128 (3)
Thermodynamic Definition of Entropy 131 (1)
The Carnot Heat Engine 131 (7)
Thermodynamic Efficiency 134 (1)
The Entropy Function 135 (1)
Refrigerators, Air Conditioners, and Heat 136 (2)
Pumps
The Second Law of Thermodynamics 138 (3)
Entropy Changes 141 (7)
Entropy Change due to Mixing of Ideal 141 (1)
Gases
Entropy Change due to Phase Transitions 142 (2)
Entropy Change due to Heating 144 (4)
The Third Law of Thermodynamics 148 (5)
Third--Law or Absolute Entropies 148 (3)
Entropy of Chemical Reactions 151 (2)
Residual Entropy 153 (4)
Statements of the Second Law of 157 (2)
Thermodynamics
Problems 159 (6)
Gibbs and Helmholtz Energies and Their 165 (38)
Applications
Gibbs and Helmholtz Energies 165 (3)
Meaning of Helmholtz and Gibbs Energies 168 (4)
Helmholtz Energy 168 (1)
Gibbs Energy 169 (3)
Standard Molar Gibbs Energy of Formation 172 (3)
(ΔfG°)
Dependence of Gibbs Energy on Temperature 175 (3)
and Pressure
Dependence of G on Temperature 175 (1)
Dependence of G on Pressure 176 (2)
Gibbs Energy and Phase Equilibria 178 (8)
The Clapeyron and Clausius--Clapeyron 180 (2)
Equations
Phase Diagrams 182 (4)
The Phase Rule 186 (1)
Thermodynamics of Rubber Elasticity 186 (5)
Some Thermodynamic Relationships 191 (3)
Derivation of the Phase Rule 194 (3)
Problems 197 (6)
Nonelectrolyte Solutions 203 (46)
Concentration Units 203 (2)
Percent by Weight 203 (1)
Mole Fraction (x) 204 (1)
Molarity (M) 204 (1)
Molality (m) 204 (1)
Partial Molar Quantities 205 (3)
Partial Molar Volume 205 (1)
Partial Molar Gibbs Energy 206 (2)
The Thermodynamics of Mixing 208 (3)
Binary Mixtures of Volatile Liquids 211 (6)
Real Solutions 217 (4)
The Solvent Component 218 (1)
The Solute Component 218 (3)
Phase Equilibria of Two--Component Systems 221 (7)
Distillation 221 (5)
Solid--Liquid Equilibria 226 (2)
Colligative Properties 228 (16)
Vapor--Pressure Lowering 228 (1)
Boiling--Point Elevation 229 (3)
Freezing- -Point Depression 232 (3)
Osmotic Pressure 235 (9)
Problems 244 (5)
Electrolyte Solutions 249 (52)
Electrical Conduction in Solution 249 (10)
Some Basic Definitions 249 (6)
Degree of Dissociation 255 (1)
Ionic Mobility 256 (2)
Applications of Conductance Measurements 258 (1)
A Molecular View of the Solution Process 259 (4)
Thermodynamics of Ions in Solution 263 (3)
Enthalpy, Entropy, and Gibbs Energy of 264 (2)
Formation of Ions in Solution
Ionic Activity 266 (5)
Debye--Huckel Theory of Electrolytes 271 (6)
The Salting--In and Salting-Out Effects 274 (3)
Colligative Properties of Electrolyte 277 (5)
Solutions
The Donnan Effect 279 (3)
Biological Membranes 282 (9)
Membrane Transport 284 (7)
Notes on Electrostatics 291 (3)
The Donnan Effect Involving Proteins 294 (3)
Bearing Multiple Chages
Problems 297 (4)
Chemical Equilibrium 301 (50)
Chemical Equilibrium in Gaseous Systems 301 (8)
Ideal Gases 301 (6)
Real Gases 307 (2)
Reactions in Solution 309 (1)
Heterogeneous Equilibria 310 (2)
The Influence of Temperature, Pressure, and 312 (6)
Catalysts on the Equilibrium Constant
The Effect of Temperature 313 (3)
The Effect of Pressure 316 (1)
The Effect of a Catalyst 317 (1)
Binding of Ligands and Metal Ions to 318 (6)
Macromolecules
One Binding Site per Macromolecule 318 (1)
n Equivalent Binding Sites per 319 (3)
Macromolecule
Equilibrium Dialysis 322 (2)
Bioenergetics 324 (14)
The Standard State in Biochemistry 325 (2)
ATP---The Currency of Energy 327 (3)
Principles of Coupled Reactions 330 (1)
Glycolysis 330 (6)
Some Limitations of Thermodynamics 336 (2)
The Relationship Between Fugacity and 338 (3)
Pressure
The Relationships Between K1 and K2 and the 341 (4)
Intrinsic Dissociation Constant K
Problems 345 (6)
Electrochemistry 351 (46)
Electrochemical Cells 351 (2)
Single--Electrode Potential 353 (3)
Thermodynamics of Electrochemical Cells 356 (7)
The Nernst Equation 360 (2)
Temperature Dependence of EMF 362 (1)
Types of Electrodes 363 (1)
Metal Electrodes 363 (1)
Gas Electrodes 363 (1)
Metal--Insoluble Salt Electrodes 363 (1)
The Glass Electrode 364 (1)
Ion--Selective Electrodes 364 (1)
Types of Electrochemical Cells 364 (2)
Concentration Cells 365 (1)
Fuel Cells 365 (1)
Applications of EMF Measurements 366 (2)
Determination of Activity Coefficients 367 (1)
Determination of pH 367 (1)
Potentiometric Titration of Redox Reactions 368 (5)
Biological Oxidation 373 (8)
The Chemiosmotic Theory of Oxidative 378 (3)
Phosphorylation
Membrane Potential 381 (10)
The Goldman Equation 384 (1)
The Action Potential 384 (7)
Problems 391 (6)
Acids and Bases 397 (48)
Definitions of Acids and Bases 397 (1)
Dissociation of Acids and Bases 398 (8)
The Ion Product of Water and the pH Scale 403 (2)
The Relationship Between the Dissociation 405 (1)
Constant of an Acid and Its Conjugate Base
Salt Hydrolysis 406 (1)
Acid--Base Titrations 407 (5)
Acid--Base Indicators 411 (1)
Diprotic and Polyprotic Acids 412 (4)
Amino Acids 416 (4)
Dissociation of Amino Acids 416 (3)
The Isoelectric Point (pI) 419 (1)
Buffer Solutions 420 (5)
The Effect of Ionic Strength and 422 (2)
Temperature on Buffer Solutions
Preparing a Buffer Solution With a 424 (1)
Specific pH
Buffer Capacity 425 (1)
Maintaining the pH of Blood 425 (6)
A More Exact Treatment of Acid-Base 431 (8)
Equilibria
Problems 439 (6)
Chemical Kinetics 445 (66)
Reaction Rate 445 (1)
Reaction Order 446 (14)
Zero--Order Reactions 447 (1)
First--Order Reactions 448 (4)
Second--Order Reactions 452 (6)
Determination of Reaction Order 458 (2)
Molecularity of a Reaction 460 (4)
Unimolecular Reactions 461 (2)
Bimolecular Reactions 463 (1)
Termolecular Reactions 463 (1)
More Complex Reactions 464 (5)
Reversible Reactions 464 (2)
Consecutive Reactions 466 (2)
Chain Reactions 468 (1)
The Effect of Temperature on Reaction Rates 469 (2)
The Arrhenius Equation 470 (1)
Potential--Energy Surfaces 471 (2)
Theories of Reaction Rates 473 (7)
Collision Theory 473 (2)
Transition--State Theory 475 (1)
Thermodynamic Formulation of 476 (4)
Transition-State Theory
Isotope Effects in Chemical Reactions 480 (3)
Reactions in Solution 483 (2)
Fast Reactions in Solution 485 (6)
The Flow Method 487 (1)
The Relaxation Method 488 (3)
Oscillating Reactions 491 (3)
Derivation of Equation 12.9 494 (2)
Derivation of Equation 12.38 496 (4)
Problems 500 (11)
Enzyme Kinetics 511 (50)
General Principles of Catalysis 511 (3)
Enzyme Catalysis 512 (2)
The Equations of Enzyme Kinetics 514 (7)
Michaelis--Menten Kinetics 515 (2)
Steady--State Kinetics 517 (2)
The Significance of KM and Vmax 519 (2)
Chymotrypsin: A Case Study 521 (3)
Multisubstrate Systems 524 (2)
The Sequential Mechanism 525 (1)
The Nonsequential or ``Ping--Pong'' 526 (1)
Mechanism
Enzyme Inhibition 526 (10)
Reversible Inhibition 527 (8)