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Table of Atomic Weights (Relative Atomic Masses)
NE 8 IN SSCL SS SL STI EA STEED ELE A IEE TSE 5A OS A AE SS SEE ETT LEIS ES ELE LETTS EE ILO EEE TE
Atomic Atomic Atomic Atomic

Name Symbol Number Weight Name Symbol Number Weight
Actinium* Ac 89 (227.028) Neodymium Nd 60 144.24(3)

Aluminum Al 13 26.98 1539(5) Neon Ne 10 20.1797(6)
Americium* Am 95 (243) Neptunium* Np 93 (237.048)
Antimony (Stibium) Sb 51 121.757(3) Nickel Ni 28 58.6934(2)
Argon Ar 18 39.948(1) Niobium Nb 41 92.90638(2)
Arsenic As 33 74.92159(2) Nitrogen N 7 14.00674(7)
Astatine* At 85 (210) Nobelium* No 102 (259)
Barium Ba 56 137.327(7) Osmium Os 76 190.23(3)
Berkelium* Bk 97 (247) Oxygen O 8 15.9994(3)
Beryllium Be 4 9.012182(3) Palladium Pd 46 106.42(1)
Bismuth Bi 83 208.98037(3) Phosphorus P 15 30.973762(4)
Bohrium* Bh 107 (262) Platinum Pt 78 195.08(3)
Boron B 5 10.811(5) Plutonium* Pu 94 (244)
Bromine Br 35 79.904(1) Polonium* Po 84 (209)
Cadmium Cd 48 112.411(8) Potassium (Kalium) K 19 39.0983(1)
Cesium Gs 55 132.90543(5) Praseodymium Pr 59 140.90765(3)
Calcium Ca 20 40.078(4) Promethium* Pm 61 (145)
Californium* CE 98 (251) Protactinium* Pa 91 231.03588(2)
Carbon Cc 6 12.011(1) Radium* Ra 88 (226.025)
Cerium Ce 58 140.115(4) Radon* Rn 86 (222)
Chlorine Cl li 35.4527(9) Rhenium Re WD 186.207(1)
Chromium Cr 24 51.9961(6) Rhodium Rh 45 102.90550(3)
Cobalt Co ai 58.93320(1) Rubidium Rb 37 85.4678(3)
Copper Cu 29 63.546(3) Ruthenium Ru 44 101.07(2)
Curium* Cm 96 (247) Rutherfordium* Rf 104 (261)
Dubnium* Db 105 (262) Samarium Sm 62 150.36(3)
Dysprosium Dy 66 162.50(3) Scandium Sc 21 44.955910(9)
Einsteinium* Es 99 (254) Seaborgium* Sg 106 (263)
Erbium Er 68 167.26(3) Selenium Se 34 78.96(3)
Europium Eu 63 151.965(9) Silicon Si 14 28.0855(3) F
Fermium* Fm 100 (257) Silver Ag 47 107.8682(2)
Fluorine F 9 18.9984032(9) Sodium (Natrium) Na 11 22.989768(6)
Francium* Fr 87 (223) Strontium Sr 38 87.62(1)
Gadolinium Gd 64 157-258) Sulfur S 16 32.066(6)
Gallium Ga 31 69.723(1) Tantalum Ta q 180.9479(1)
Germanium Ge 32 72.61(2) Technetium* Te 43 (98)
Gold Au 79 196.96654(3) Tellurium Te 52, 127.60(3)
Hafnium Hf a2 178.49(2) Terbium Tb 65 158.92534(3)
Hassium* Hs 108 (265) Thallium Tl 81 204.3833(2)
Helium He 2 4.002602(2) Thorium* Th 90 232.0381(1)
Holmium Ho 67 164.93032(3) Thulium Tm 69 168.93421(3)
Hydrogen H 1 1.00794(7) Tin Sn 50 118.710(7)
Indium In 49 114.818(3) Titanium aly 22 47.88(3)
Todine I 53 126.90447(3) Tungsten (Wolfram) Ww 74 183.84(1)
Iridium Ir ey) 192.22(3) Ununbium* Uub 112 (277)
Iron Fe 26 55.847(3) Ununhexium Uuh 116 (289)
Krypton Kr 36 83.80(1) Ununnilium* Uun 110 (269)
Lanthanum La 57, 138.9055(2) Ununoctium Uuo 118 (293)
Lawrencium* Ge 103 (262) Ununquadium Uuq 114 (285)
Lead Pb 82 207.2(1) Unununium* Uuu 111 (272)
Lithium Li 3 6.941(2) Uranium* U 92 238.0289(1)
Lutetium Lu 71 174.967(1) Vanadium Vv 23 50.9415(1)
Magnesium Mg 12 24.3050(6) Xenon Xe 54 131.29(2)
Manganese Mn 25 54.93805(1) Ytterbium Yb ~ 70 173.04(3)
Meitnerium* Mt 109 (266) Yttrium Y 39 88.90585(2)
Mendelevium* Md 101 (258) Zinc Zn 30 65.39(2)
Mercury Hg 80 200.59(2) Zirconium Zr 40 91.224(2)
Molybdenum Mo 42 95.94(1)
*The elements marked with an asterisk have no stable isotopes.

Recommended by the IUPAC Commission on Atomic Weights and Atomic Abundances; further details are to be found in “Atomic weights of the elements
1991,” Pure and Applied Chemistry, 64, 1519-1534(1992). The values are reliable to + the figure given in parentheses, applicable to the last digit. Numbers for
atomic weights in parentheses are estimates.
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BROOKS/COLE
CENGAGE Learning”
Physical Chemistry, Fourth Edition © 2003 Brooks/Cole, Cengage Learning

Keith J. Laidler, John H. Meiser, Brian C. Sanctuary
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ey S) i)tik ish leh8) el
CONTENTS
Preface xii Equations of State 36

The van der Waals Equation of State 36 The Law of
Corresponding States 38 Other Equations of State 40
The Nature of Physical Chemistry and
1.14 The Virial Equation 41
the Kinetic Theory of Gases 1
Appendix: Some Definite and Indefinite Integrals
Often Used in Physical Chemistry 43
al The Nature of Physical Chemistry 3 Key Equations 43 Problems 44
f Some Concepts from Classical Suggested Reading 48
Mechanics 4
2.
Work 4 Kinetic and Potential Energy 5 The First Law
ee) Systems, States, and Equilibrium 6 of Thermodynamics 49
1.4 Thermal Equilibrium 7
The Concept of Temperature and Its Measurement 8
oan Origins of the First Law 51
1 Pressure and Boyle’s Law 8 22 States and State Functions 52
Biography: Robert Boyle 11
2.3 Equilibrium States and Reversibility 53
1.6 Gay-Lussac’s (Charles’s) Law 12
2.4 Energy, Heat, and Work 54
ua The Ideal Gas Thermometer 13
The Nature of Work 56 Processes at Constant
1.8 The Equation of State for an Ideal Gas_ 15 Volume 59 Processes at Constant Pressure: Enthalpy 59
Heat Capacity 60
The Gas Constant and the Mole Concept 15
aco) The Kinetic-Molecular Theory of Ideal 2.5 Thermochemistry 62

Gases -17 Extent of Reaction 62 Standard States 64
Measurement of Enthalpy Changes 65 Calorimetry 67
The Pressure of a Gas Derived from Kinetic Theory 18
Relationship between AU and AH 67 Temperature
Kinetic Energy and Temperature 19 Dalton’s Law
Dependence of Enthalpies of Reaction 68 — Enthalpies of
of Partial Pressures 21 Graham’s Law of Effusion 22
Formation 71 Bond Enthalpies 73
Molecular Collisions 23
2.6 Ideal Gas Relationships 74
1.10 The Barometric Distribution Law 27
Reversible Compression at Constant Pressure 74
at The Maxwell Distribution of Molecular Reversible Pressure Change at Constant Volume 76
Speeds and Translational Energies 29 Reversible Isothermal Compression 77 Reversible
The Distribution of Speeds 29 The Distribution of Adiabatic Compression 79
Translational Energy 32 Zu, Real Gases 81
Real Gases 33 The Joule-Thomson Experiment 81 Van der Waals
The Compression Factor 33 Condensation of Gases: The Gases 84
Critical Point 33. Uses of Supercritical Fluids 35 Key Equations 86 Problems 86
Suggested Reading 91
vi Contents
The Second and Third Laws 4.3 Chemical Equilibrium in Solution 160
of Thermodynamics 92 4.4 Heterogeneous Equilibrium 162
4.5 Tests for Chemical Equilibrium 163
Biography: Rudolf Julius Emmanuel Clausius 95 4.6 Shifts of Equilibrium at Constant
oa The Carnot Cycle 96 Temperature 164
Efficiency of a Reversible Carnot Engine 100 Carnot’s 4.7 Coupling of Reactions 166
Theorem 101 The Thermodynamic Scale of 4.8 Temperature Dependence of Equilibrium
Temperature 102 The Generalized Cycle: The Concept
Constants 169
of Entropy 103
4.9 Pressure Dependence of Equilibrium
D2 Irreversible Processes 104
Constants 172
3.3 Molecular Interpretation of Entropy 106 Key Equations 174 Problems 174
3.4 The Calculation of Entropy Changes 109 Suggested Reading 179
Changes of State of Aggregation 109 — Ideal Gases 110

Entropy of Mixing 112 — Informational or Configurational
Entropy 113. Solids and Liquids 114
2 _. Phases and Solutions 180
3.5 The Third Law of Thermodynamics 117
Cryogenics: The Approach to Absolute Zero 117
5.1 Phase Recognition 182
Absolute Entropies 119 Phase Distinctions in the Water System 182 Phase
Changes in Liquid Crystals 183 Phase Equilibria in a
3.6 Conditions for Equilibrium 120 One-Component System: Water 184
Constant Temperature and Pressure: The Gibbs Energy 122
Constant Temperature and Volume: The Helmholtz
5.2 Vaporization and Vapor Pressure 187
Energy 123 Thermodynamics of Vapor Pressure: The Clapeyron
Equation 187 The Clausius-Clapeyron Equation 189
Om, The Gibbs Energy 123 Enthalpy and Entropy of Vaporization: Trouton’s Rule 191
Molecular Interpretation 123 Gibbs Energies of Variation of Vapor Pressure with External Pressure 193
Formation 125 Gibbs Energy and Reversible Work 126
5.3 Classification of Transitions in Single-
3.8 Some Thermodynamic Relationships 127 Component Systems 194
Maxwell Relations 128 Thermodynamic Equations of 5.4 Ideal Solutions: Raoult’s and Henry’s
State 129 Some Applications of Thermodynamic
Relationships 130 Fugacity and Activity 132
Laws 196
5.5 Partial Molar Quantities 199
3.9 The Gibbs-Helmholtz Equation 135
Relation of Partial Molar Quantities to Normal
3.10 Thermodynamic Limitations to Energy Thermodynamic Properties 201
Conversion 136
5.6 The Chemical Potential 203
First Law Efficiencies 136 Second Law Efficiencies 136
Refrigeration and Liquefaction 137 Heat Pumps 139 Dae Thermodynamics of Solutions 205
Chemical Conversion 140 Raoult’s Law Revisited 205 Ideal Solutions 207
Key Equations 142 Problems 143 Nonideal Solutions; Activity and Activity Coefficients 209
5.8 The Colligative Properties 211
Freezing Point Depression 211 — Ideal Solubility and
the Freezing Point Depression 214 Boiling Point
we
4_ Chemical Equilibrium 149 Elevation 215 Osmotic Pressure 216
Key Equations 218 Problems 219
Biography: Jacobus Henricus van’t Hoff 152
4.1 Chemical Equilibrium Involving Ideal
Gases 153 6 Phase Equilibria 223
Equilibrium Constant in Concentration Units 155 — Units
of the Equilibrium Constant 157 6.1 Equilibrium Between Phases 225
4.2 Equilibrium in Nonideal Gaseous Number of Components 225 Degrees of Freedom 227
Systems 160 The Phase Rule 227
Contents Vii
6.2 One-Component Systems 228 7.9 Theories of lons in Solution 296

6.3 Binary Systems Involving Vapor 229 Drude and Nernst’s Electrostriction Model 296 Born’s
Model 296 More Advanced Theories 298 Qualitative
Liquid- Vapor Equilibria of Two-Component Systems 229
Treatments 298
Liquid-Vapor Equilibrium in Systems Not Obeying Raoult’s
Law 233 Temperature-Composition Diagrams: Boiling 7.10 Activity Coefficients 300
Point Curves 233 Distillation 234 Azeotropes 237 Debye-Hiickel Limiting Law 300 Deviations from the
Distillation of Immiscible Liquids: Steam Distillation 239 Debye-Hiickel Limiting Law 303
Distillation of Partially Miscible Liquids 240
Teli lonic Equilibria 304
6.4 Condensed Binary Systems 241 Activity Coefficients from Equilibrium Constant
Two-Liquid Components 241 — Solid-Liquid Equilibrium: Measurements 304 Solubility Products 305
Simple Eutectic Phase Diagrams 243
lonization of Water 307
6.5 Thermal Analysis 244 The Donnan Equilibrium 308
6.6 More Complicated Binary Systems 245 Key Equations 310 Problems 311
Solid Solutions 247 Partial Miscibility 248 Suggested Reading 314
Compound Formation 249
6.7 Crystal Solubility: The Krafft Boundary and Electrochemical Cells oS

Krafft Eutectic 250
6.8 Ternary Systems 252
The Daniell Cell 317
Liquid-Liquid Ternary Equilibrium 252 — Solid-Liquid
Equilibrium in Three-Component Systems 253 Standard Electrode Potentials 319
Representation of Temperature in Ternary Systems 255 The Standard Hydrogen Electrode 319 Other Standard
Key Equations 256 Problems 257 Electrodes 323 _Ion-Selective Electrodes 324
8.3 Thermodynamics of Electrochemical
Cells 325
ah_ Solutions of Electrolytes 263 The Nernst Equation 330 Nernst Potentials 332
Temperature Coefficients of Cell emfs 335
8.4 Types of Electrochemical Cells 336
Electrical Units 266
Concentration Cells 337 Redox Cells 338
TA Faraday’s Laws of Electrolysis 267
8.5 Applications of emf Measurements 341
Biography: Michael Faraday 268
pH Determinations 341 Activity Coefficients 341
a2 Molar Conductivity 269 Equilibrium Constants 342 Solubility Products 343
Potentiometric Titrations 344
73 Weak Electrolytes: The Arrhenius
Theory 272 8.6 Fuel Cells 345
Biography: Svante August Arrhenius 273 8.7 Photogalvanic Cells 346
Ostwald’s Dilution Law 273 8.8 Batteries, Old and New 348
7.4 Strong Electrolytes 274 The Original and Modified Leclanché Cell 349 — Alkaline
Manganese Cells 350 Zinc—Mercuric Oxide and
Debye-Hiickel Theory 275 The Ionic Atmosphere 276
Zinc—Silver Oxide Batteries 350 Metal-Air Batteries
Mechanism of Conductivity 281 Ion Association 283
85 Nickel-Cadmium (Nicad) Secondary Battery 352
Conductivity at High Frequencies and Potentials 284
The Lead-Acid Storage Battery 352 Lithium Ion
Uae) Independent Migration of lons 285 Batteries 353 -
Ionic Mobilities 286 Key Equations 355 Problems 356
7.6 Transport Numbers 286
Hittorf Method 288 Moving Boundary Method 290
Chemical Kinetics I.
Tat lon Conductivities 291
The Basic Ideas 361
Ionic Solvation 292 Mobilities of Hydrogen and
Hydroxide Ions 292 Ionic Mobilities and Diffusion
Coefficients 293 Walden’s Rule 294
9.1 Rates of Consumption
7.8 Thermodynamics of lons 294 and Formation 363
Viii Contents
92 Rate of Reaction 363 10.6 Photochemical Reactions 437

9.3 Empirical Rate Equations 364 The Photochemical Hydrogen-Chlorine Reaction 440
The Photochemical Hydrogen-Bromine Reaction 441
Order of Reaction 365 Reactions Having No Order 366
Photosensitization 442 Flash Photolysis 442
Rate Constants and Rate Coefficients 366
9.4 Analysis of Kinetic Results 367 10.7 Radiation-Chemical Reactions 443
Method of Integration 368 Half-Life 371 Differential 10.8 Explosions 445

Method 372 Reactions Having No Simple Order 373 The Initiation of an Explosion 446 The Transmission of
Opposing Reactions 373 an Explosion 446 Detonations 447 —_Explosion Limits
3D Techniques for Very Fast Reactions 374 in Gaseous Explosions 447 Cool Flames 448
Flow Methods 374 Pulse Methods 376 10.9 Catalysis 449

9.6 Molecular Kinetics 379 Acid-Base Catalysis 450 Brgnsted Relationships 453
Enzyme Catalysis 454
Molecularity and Order 379
Oy The Arrhenius Equation 380 10.10 Reactions in Solution: Some Special

Activation Energy 383 Features 459
9.8 Potential-Energy Surfaces 385 Collisions and Encounters 459
9.9 The Preexponential Factor 388 10211 Mechanisms of Polymerization in

Hard-Sphere Collision Theory 388 Transition-State Macromolecules 460
Theory 390 Introduction 460 Addition Polymers 461 — Step-
Biography: Henry Eyring 391 Growth Polymerization 462 Ionic Polymerizations 462
“Living” Polymers 463 Heterogeneous Polymerization
Quantum-Mechanical Tunneling 395 Kinetic-Isotope
464 Emulsion Polymerization 464
Effects 395
9.10 Reactions in Solution 396 10.12 Kinetics of Polymerization 465

Influence of Solvent Dielectric Constant 397 Influence
Free-Radical Polymerization 465 Condensation
Polymerization 467
of Ionic Strength 401 —_ Influence of Hydrostatic
Pressure 402 Diffusion-Controlled Reactions 404 10.13 Induction Periods, Oscillations,
Linear Gibbs Energy Relationships 404
and Chaos 468
ol Reaction Dynamics 405 Clock Reactions 468 Oscillating Reactions 469 Cool
Molecular Beams 406 Chemiluminescence 407 Flames 470 The Belousov-Zhabotinsky Reaction 471
Dynamical Calculations 408 — The Detection of Transition Chaos in Chemical Reactions 475
Species 408
Key Equations 409 Problems 409 Suggested
10.14 Electrochemical Dynamics 476
Reading 414 Kinetics of Electrode Reactions 477 Polarography 481
Electrokinetic Effects: The Electric Double Layer 483
1(
Electroosmosis 485 Electrophoresis 486 Reverse
Chemical Kinetics II. Composite Isoelectric Effects 487
Mechanisms 416 Problems 487 Suggested Reading 493
10.1
10.2
Evidence for a Composite
Mechanism 421
Types of Composite Reactions 422
1 Quantum Mechanics and Atomic
Structure 494
10.3 Rate Equations for Composite

HE Electromagnetic Radiation and the Old
Mechanisms 423
Quantum Theory 496
Consecutive Reactions 423 Steady-State Treatment 425
Rate-Controlling (Rate-Determining) Steps 426 Simple Harmonic Motion 497 Plane Waves and Standing
Waves 500 Blackbody Radiation 503 _ Einstein
10.4 Rate Constants, Rate Coefficients, and and the Quantization of Radiation 507 Zero-Point
Equilibrium Constants 429 Energy 509
10.5 Free-Radical Reactions 431 2 Bohr’s Atomic Theory 509

Chain Reactions 432 Organic Decompositions 434 Spectral Series 511
Contents ix
11.3 The Foundations of Quantum 12.2 The Hydrogen Molecule 583

Mechanics 513 The Heitler-London Valence-Bond Method 583
The Wave Nature of Electrons 514 The Uncertainty Electron Spin 589 The Molecular-Orbital
Principle 516 Method 589
11.4 Schrddinger’s Wave Mechanics 518 12.3 Huckel Theory for More Complex
Eigenfunctions and Normalization 521 Molecules 594
Ethylene 596 Butadiene 596 Benzene 599
Us Quantum-Mechanical Postulates 522
Orthogonality of Wave Functions 526 —Non-
12.4 Valence-Bond Theory for More Complex
Commutation and the Heisenberg Uncertainty Molecules 600
Principle 527 The Covalent Bond 600 Electronegativity 601
Orbital Overlap 603 Orbital Hybridization 604
11.6 Quantum Mechanics of Some Simple
Multiple Bonds 607
Systems 528
The Free Particle 529. The Particle ina Box 530
12.5 Symmetry in Chemistry 608
The Harmonic Oscillator 535 Symmetry Elements and Symmetry Operations 609
Point Groups and Multiplication Tables 613. Group
ne Quantum Mechanics of Hydrogenlike Theory 618
Atoms 537
12.6 Symmetry of Molecular Orbitals 621
Solution of the ® Equation 539 Solution of the ©
Homonuclear Diatomic Molecules 622 The Weakest
Equation 540 Solution of the R Equation 541
Known Bond: The Helium Dimer 626 —_Heteronuclear
Complete Wave Functions 542
Diatomic Molecules 627 The Water Molecule 628
11.8 Physical Significance of the Orbital Key Equations 631 Problems 632 Suggested
Quantum Numbers 544 Reading 634
The Principal Quantum Number n 545 — Angular
7
Dependence of the Wave Function: The Quantum
Numbers / and m, 548
Foundations of Chemical
Spectroscopy 636
Angular Momentum and Magnetic
_—
ch9
Moment 550
Angular Momentum 550 Magnetic Moment 553 Asad Emission and Absorption Spectra 638
Classical Electromagnetic Waves 638 The Energy of
11.10 The Rigid Linear Rotor 555
Radiation in Emission and Absorption 639 = Time-
iia Spin Quantum Numbers 556 Dependent Perturbation Theory and Spectral Transitions
640 The Einstein Coefficients 643 The Laws of
qh ay 4 Many-Electron Atoms 558
Lambert and Beer 645
The Pauli Exclusion Principle 558 The Aufbau
Principle 561 Hund’s Rule 562 Agee Atomic Spectra 648
Coulombic Interaction and Term Symbols 648
11.13 Approximation Methods in Quantum
Biography: Gerhard Herzberg 649
Mechanics 563
Exchange Interaction: Multiplicity of States 651 Spin-
The Variation Method 564 Perturbation Method 566
Orbit Interactions 654 The Vector Model of the
The Self-Consistent Field (SCF) Method 567 Slater
Atom 656 The Effect of an External Magnetic
Orbitals 568 Relativistic Effects in Quantum
Field 658
Mechanics 569 Dirac Notation 569
Key Equations 571 Problems 572 13.3 Pure Rotational Spectra of Molecules 663
Suggested Reading 575 Diatomic Molecules 665 Linear Triatomic
Molecules 669 Microwave Spectroscopy 670
Nonlinear Molecules 671 The Stark Effect 673
if The Chemical Bond 576
+
13.4 Vibrational-Rotational Spectra
of Molecules 673
The Nature of the Covalent Bond 578 Diatomic Molecules 673 Coupling of Rotational and
Biography: Gilbert Newton Lewis 579 Vibrational Motion: The Separability Assumption 679
Normal Modes of Vibration 681 — Infrared Spectra of
12.1 The Hydrogen Molecular-lon Complex Molecules 683 Characteristic Group
H,* 580 Frequencies 686
Contents
Raman Spectra 687 14.12 Mass Spectrometry 775

Electronic Spectra of Molecules 691 Key Equations 778 Problems 778 Suggested
Reading 779
Term Symbols for Linear Molecules 692 Selection
Rules 695 The Structure of Electronic Band
Systems 698 Excited Electronic States 700 13 _ Statistical Mechanics 781
The Fate of Electronically Excited Species 704
Appendix: Symmetry Species Corresponding

to Infrared and Raman Spectra 707 Maxwell’s Demon 783
Key Equations 708 Problems 708 Suggested dont Forms of Molecular Energy 784
Reading 712 Molar Heat Capacities of Gases: Classical
Interpretations 786
Some Modern Applications Biography: Ludwig Boltzmann 788

Molar Heat Capacities of Gases: Quantum Restrictions 789
= of Spectroscopy 714
15:2 Principles of Statistical Mechanics 789
The Boltzmann Distribution Law 793
14.1 Laser Spectroscopy 716
15:3 The Partition Function 795
Requirements for Stimulated Emission 717 _ Properties of
Laser Light 718 Three-and Four-Level Lasers 719 The Molecular Partition Function 795 The Canonical
Partition Function 797
14.2 Spectral Line Widths 720
Lifetime Broadening 720 Doppler Broadening 721
15.4 Thermodynamic Quantities from Partition
Functions 798
14.3 Types of Lasers 721
loys The Partition Function for Some Special
14.4 Laser Techniques for Chemistry 724
Cases 802
The Use of Lasers in Chemical Spectroscopy 727 Laser
Translational Motion 802 Rotational Motion 804
Raman Spectroscopy 728 | Hyper-Raman Spectroscopy
Vibrational Motion 806 The Electronic Partition
728 Resonancce Raman Spectroscopy 729 Coherent
Function 809 The Nuclear Partition Function 810
Anti-Stokes Raman Scattering (CARS) 730 — Laser-
Induced Fluorescence (LIF) 730 Zero Kinetic Energy 15.6 The Internal Energy, Enthalpy, and Gibbs
Roman Spectroscopy (ZEKE) 731 Application of Lasers Energy Functions 811
to Other Branches of Spectroscopy 731
15.7 The Calculation of Equilibrium
14.5 Magnetic Spectroscopy 733
Constants 813
Magnetic Susceptibility 733 Magnetic and Electric
Direct Calculation from Partition Functions 815
Moments 734 Magnetic Interaction Leading to Spectra
Consequences 736 15.8 Transition-State Theory 819
14.6 Nuclear Magnetic Resonance The Assumption of “Quasi-Equilibrium” 819
Spectroscopy 738 Derivation of the Transition-State Theory Equation 820
Thermodynamic Formulation of Transition-State
The Machinery of NMR Spectroscopy 741 Pulsed NMR
Theory 825 Extension of Transition-State Theory 825
741 ~~ Spin Echoes 743 NMR Instrumentation 745
One-Dimensional NMR Experiments 746 Chemical 15.9 The Approach to Equilibrium 826
Shifts 747 J-coupling 748 TwoCoupledSpins 748
15,10 The Canonical Ensemble 828
Classification of Spectra 751 Two-Dimensional
NMR752 Examples of the Use of NMR in Chemistry 757 Key Equations 829 Problems 830 Suggested
Solid-State NMR 758 Reading 833
14.7 Electron Magnetic Resonance (EMR) 760

Hyperfine structure 762 76 The Solid State 835
14.8 Mossbauer Spectroscopy 765
14.9 Photoelectron Spectroscopy 767 16:1 Crystal Forms and Crystal Lattices 837
14.10 Photoacoustic Spectroscopy 770 The Unit Cell 838 Symmetry Properties 840
Point Groups and Crystal Systems 842 Space
14.11 Chiroptical Methods 770 Lattices 842 Space Groups 844 Periodicity and the
The Nature of Polarized Light 770 Optical Activity and Reciprocal Lattice 845 Crystal Planes
Polarimetry 771 Optical Rotatory Dispersion (ORD) and Miller Indices 846 Indices of Direction 849
774 ~~ Circular Dichroism (CD) 774
Contents Xi
16.2 X-Ray Crystallography 850 Forces 915 Repulsive Forces 915 Resultant
Intermolecular Energies 915
The Origin of X Rays 850 The Bragg Equation 852
X-Ray Scattering 854 Elastic Scattering, Fourier 17.4 Theories and Models of Liquids 916
Analysis, and the Structure Factor 856
Free-Volume or Cell Theories 917. —_Hole or “Significant
16.3. Experimental Methods Structure” Theories 920 Partition Functions for
and Applications 859 Liquids 920 Computer Simulation of Liquid
Behavior 920
The Laue Method 859 The Powder Method 859
Rotating Crystal Methods 860 X-Ray Diffraction 861 17.5 Water, the Incompar able Liquid 921
Biography: Dorothy Crowfoot Hodgkin 862 Experimental Investigations of Water Structure 922
Electron Diffraction 863 Neutron Diffraction 864 Intermolecular Energies in Water 923 Models of
Interpretation of X-Ray Diffraction Patterns 864 Liquid Water 923 Compu ter Simulation of Water
Structure Factor for a Simple Cubic (sc) Lattice 865 Structure 924
Structure Factor for a Face-Centered Cubic (bec) Lattice
865 Structure Factor for a Body-Centered (fcc)
17.6 The Hydrophobic Effect 924
Lattice 866 Key Equations 925 Problems 926 Suggested
Reading 928
16.4 Theories of Solids 867
Bonding in Solids 868 Ionic, Covalent, and
van der Waals Radii 868 — Binding Energy of Ionic
Crystals 869 The Born-Haber Cycle 870 The Surface Chemistry and Colloids 929
Structure of Metals: The Closest Packing of Spheres 872
Metallic Radi 873
Adsorption 931
16.5 Statistical Thermodynamics of Crystals:
Theories of Heat Capacities 874 Adsorption Isotherms 933
The Einstein Model 875 The Debye Model 876 The Langmuir Isotherm 933 Adsorption with
Fermi-Dirac Statistics 877 Visualization of the Dissociation 935 Competitive Adsorption 936
Quantum Statistics Function 877. Quantum Other Isotherms 937
Statistics 878 Determination of the Fermi
18.3 Thermodynamics and Statistical
Energy 880
Mechanics of Adsorption 938
16.6 Electrical Conductivityin Solids 883
18.4 Chemical Reactions on Surfaces 940
Metals: The Free-Electron Theory 884 Metals,
Semiconductors, and Insulators: Band Theory 885 p-n Unimolecular Reactions 940 Bimolecular Reactions 941
junction 889 Superconductivity 890
18.5 Surface Heterogeneity 943
16.7. Optical Properties of Solids 892
18.6 The Structure of Soli d Surfaces
Transition Metal Impurities and Charge Transfer 893
Color and Luster in Metal 893 Color Centers:
and of Adsorbed Layers 944
Nonstoichiometric Compounds 893 Luminescence in Photoelectron Spectroscopy (XPS and UPS) 945
Solids 894 Key Equations 894 Problems 895 Field-Ion Microscopy (FIM) 945 Auger Electron
Suggested Reading 897 Spectroscopy (AES) 946 Low-Energy Electron
Diffraction (LEED) 946 — Scanning Tunneling
Microscopy (STM) 947 Details of the Solid
Surface 948
7vA The Liquid State 899
18.7 Surface Tension and Capillarity 948
17.1 Liquids Compared with Dense Gases 901 18.8 Liquid Films on Surfaces 951
Internal Pressure 902 Internal Energy 903 Biography: Agnes Pockels 953
17.2 Liquids Compared with Solids 906 18.9 Colloidal Systems 955
Radial Distribution Functions 907 X-Ray Lyophobic and Lyophilic Sol s 956 Light Scattering by
Diffraction 908 Neutron Diffraction 909 Colloidal Particles 957 Electrical Properties of Colloidal
Glasses 909 Systems 958 Gels 960 Emulsions 961
17.3. Intermolecular Forces 910
Reading 964
Ion-Ion Forces 910 Jon-Dipole Forces 911 _ Dipole-
Dipole Forces 913 Hydrogen Bonds 914 _ Dispersion
xii Contents
Appendix A Units, Quantities, and

Symbols: The SI/IUPAC
19 . Transport Properties 966
Recommendations 999
aos Viscosity 968

Appendix B_ Physical Constants 1013
Measurement of Viscosity 969 Viscosities of Gases 970 Appendix C Some Mathematical
Viscosities of Liquids 973 Viscosities of Solutions 976
Relationships 1015
1922 Diffusion 977
Appendix D Standard Enthalpies, Entropies,
Fick’s Laws 977 Solutions of Diffusion Equations 978
Brownian Movement 980 _ Self-Diffusion of Gases 983 and Gibbs Energies of Formation
Driving Force of Diffusion 984 — Diffusion and Ionic 1019
Mobility 985 Stokes’s Law 987 _ Perrin’s Experiments
on Brownian Movement 988 Diffusion through Appendix E Character Tables for Some
Membranes 989
Important Symmetry Groups in
193 Sedimentation 990 Chemistry 1028
Sedimentation Velocity 990 Sedimentation
Equilibrium 993 Answers to Problems 1035
Reading 998 1047
PREFACE
This fourth edition of Physical Chemistry, like its predecessors, has been written in
such a way as to be a suitable introduction for students who intend to become
chemists, and also for the many others who find physical chemistry essential in their
careers. The field of physical chemistry has now become so broad that it has invaded
all of the sciences. Physicists, engineers, biologists, and workers in the medical sci-
ences—all find a knowledge of physical chemistry to be important in their work.
The students for which this book is intended are assumed to have a basic
knowledge of chemistry such as they usually gain in their first year at a North
American university. (In the British system, where the science degree is usually
gained after three years, this basic material is taught in the high schools.) This book
is intended primarily for the conventional full-year course at a university. However,
it covers a good deal more than can be included in a one-year course. It may there-
fore also be useful in more advanced courses and as a general reference book for
those working in fields that require a basic knowledge of the subject.
Changes in This Edition

In this fourth edition of our book we have preserved much of the material of the for-
mer editions, making changes only to improve understanding of the concepts or
include some of the latest discoveries in physical chemistry. Many chapters have new
sections and the coverage of several chapters has been greatly expanded. Unfortu-
nately, in order to save space, we had to delete Chapter 20, Macromolecules. Because
of the importance of some ideas in that chapter to other areas of physical chemistry,
we have, however, transferred that material to other appropriate chapters.
Most of the numerical values for fundamental properties had to be adjusted in
the light of recent data. A major new addition to thermodynamic data has been
made in Appendix D; in addition, a table of CODATA thermodynamic data has
been added that includes values for H°(298.15 K) — H°(O). The data in Appendix D
relate to data at | bar pressure.
A number of new problems are included in the fourth edition, giving instruc-
tors ample choices for their students. The sets of problems cover a wide range of
subject matter and difficulty. This new edition, as well as its accompanying Solu-
tions Manual, has been thoroughly checked for accuracy.
With this edition, we are pleased to introduce a particularly useful way to visual-
ize physical processes. The CD included with this text allows the student to utilize
many interactive graphs of physical relationships. The user can ascertain the effect of
changing a variable in what might be a complex relationship. In addition, many fig-
ures are animated and give a clear understanding of difficult concepts. Included
xiii
XiV Preface
dialogue, textual information, and text links give the student a well rounded way to
learn.
As always, we welcome receiving student and other user comments and sug-
gestions for future editions. We look forward to your input.
Special Features
We have deliberately given a distinctive historical flavor to the book, in part be-
cause the history of the subject is of special interest to many students. More
importantly, we are convinced that many scientific topics are more comprehensible
if they are introduced with some regard to the way in which they originally came to
be understood. For example, attempts to present the laws of thermodynamics as
postulates are in our opinion unsatisfactory from the pedagogical point of view. A
presentation in terms of how the laws of thermodynamics were deduced from the
experimental evidence is, we think, much easier for students to understand. In addi-
tion, by seeing the historical development of a subject we learn more about the
scientific method than we can learn in any other way.
We realize that an historical approach may be dubbed “old-fashioned,” but
fashion must surely give way to effectiveness. We have also included eleven short
biographies of scientists, chosen not because we think their work more important
than that of others (for who is able to make such a judgment?), but because we find
their lives and careers to be of particular interest.
Several special aids are provided for the student in this book. New to this edi-
tion is the Objectives section listing key ideas or techniques that the student should
have mastered after finishing the chapter. The Preview of each chapter describes the
material to be presented in a brief narrative that gives a sense of unity to the mater-
ial of the chapter. All new terms are in italics or in boldface type. Particular
attention should be paid to these terms as well as to the equations that are boxed for
special emphasis. Key equations that appear in the chapter occur in a concise listing
at the end of each chapter. The mathematical relationships provided in Appendix C
should prove useful as a handy reference.
Organization and Flexibility

The order in which we have treated the various branches of physical chemistry is a
matter of personal preference; other teachers may prefer a different order. The book
has been written with flexibility in mind. The subject matter may be grouped into
the following topics:
A. Chapters 1-6: General properties of gases, liquids, and solutions; ther-

modynamics; physical and chemical equilibrium
B. Chapters 7-8: Electrochemistry
C. Chapters 9-10: Chemical kinetics
D. Chapters 11-15: Quantum chemistry; spectroscopy; statistical mechanics
E. Chapters 16-19: Some special topics: solids, liquids, surfaces, transport
properties
Our sequence has the advantage that the more difficult topics of Chapters 11-15
can come at the beginning of the second half of the course. The book also lends it-
self without difficulty to various alternative sequences, such as the following:
Preface XV
A B C
Chapters 1-6 Chapters 1-6 Chapters 1-6
Aside from this, the order of topics in some of the chapters, particularly those in
Chapters 16-19, can be varied.
End-of-Chapter Material
The Key Equation section lists equations with which the student should become
thoroughly familiar. This listing should not be construed as the only equations that
are important but rather as foundation expressions that are widely applicable to
chemical problems. The Problems have been organized according to subject matter,
and the more difficult problems are indicated with an asterisk. Answers to all prob-
lems are included at the back of the book, with detailed solutions provided in a
separate Solutions Manual for Physical Chemistry.
Units and Symbols

We have adhered to the Systéme International d’ Unités (SI) and to the recommenda-
tions of the International Union of Pure and Applied Chemistry (IUPAC), as
presented in the IUPAC “Green Book”; the reader is referred to Appendix A for an
outline of these units and recommendations. The essential feature of these recom-
mendations is that the methods of quantity algebra (often called “quantity calculus”)
are used; a symbol represents a physical quantity, which is the product of a pure num-
ber (the value of the quantity) and a unit. Sometimes, as in taking a logarithm or
making a plot, one needs the value of a quantity, which is simply the quantity divided
by the unit quantity. The IUPAC Green Book has made no recommendation in this
regard, and we have made the innovation of using in the earlier chapters a superscript
u (for unitless) to denote such a value. We felt it unnecessary to continue the practice
in the later chapters, as the point would be soon appreciated.
Acknowledgments
We are particularly grateful to a number of colleagues for their stimulating conver-
sations, help, and advice over many years, in particular: from the National Research
Council of Canada, Drs. R. Norman Jones and D. A. Ramsay (spectroscopy); from
the University of Ottawa, Dr. Glenn Facey (NMR spectroscopy), Dr. Brian E. Con-
way (electrochemistry), and Dr. Robert A. Smith (quantum mechanics); from the
University of South Dakota, Dr. Donald Abraham (physics); from Beloit College,
Dr. David A. Dobson (physics); from Argonne National Laboratory, Dr. Mark A.
Beno (X-ray spectroscopy), Drs. Michael J. Pellin and Stephen L. Dieckman (spec-
troscopy), and Dr Victor A. Maroni (solid state and superconductors); from John
Carroll University, Dr. Michael J. Setter (electrochemistry); from Ball State Univer-
sity, Dr. Jason W. Ribblett (spectroscopy and quantum mechanics); from the
University of York, Drs. Graham Doggett, Tom Halstead, Ron Hester, and Robin
Xvi Preface
Perutz; from McGill University, Drs. John Harrod, Anne-Marie Lebuis (X-ray spec-
troscopy), David Ronis, Frederick Morin, Zhicheng (Paul) Xia (NMR
spectroscopy), and Nadim Saade (mass spectroscopy).
Special acknowledgment is due to those who have contributed to the multime-
dia component of this work: Dr. Tom Halstead, University of York; Adam Halstead,
Emily Cranston, and Jiirgen Karir, MCH Multimedia Inc.; M. S. Krishnan, Institute
of Technology, Madras, India; J. Anantha Krishnan, Pronexus Infoworld, Anima-
tions.
Thanks are also due our reviewers for this edition, including:
Edmund Tisko, University of Nebraska

Gordon Atkinson, University of Oklahoma
Bernard Laurenzi, University of Albany
Stephen Kelty, Seton Hall University
Pedro Muino, Saint Francis College
Ruben Parra, University of Nebraska, Lincoln
Jonathan Kenny, Tufts University
James Whitten, University of Massachusetts, Lowell
Therese Michels, Dana College
Renee Cole, Missouri State University
Robert Brown, Douglas College
Phillip Pacey, Dalhousie University
Christine Lamont, University of Huddersfield
Curt Wentrup, University of Queensland
N.K. Singh, University of New South Wales
David Hawkes, Lambuth University
In addition, we would like to thank the following reviewers for their sugges-
tions in the previous edition: William R. Brennen (University of Pennsylvania),
John W. Coutts (Lake Forest College), Nordulf Debye (Towson State University),
D. J. Donaldson (University of Toronto), Walter Drost-Hansen (University of Mi-
ami), David E. Draper (Johns Hopkins University), Darrel D. Ebbing (Wayne State
University), Brian G. Gowenlock (University of Exeter), Robert A. Jacobson (Iowa
State University), Gerald M. Korenowski (Rensselaer Polytechnic Institute), Craig
C. Martens (University of California, Irvine), Noel L. Owen (Brigham Young Uni-
versity), John Parson (The Ohio State University), David W. Pratt (University of
Pittsburgh), Lee Pederson (University of North Carolina at Chapel Hill), Richard A.
Pethrick (University of Strathclyde), Mark A. Smith (University of Arizona),
Charles A. Trapp (University of Louisville), Gene A. Westenbarger (Ohio Univer-
sity), Max Wolfsberg (University of California, Irvine), John D. Vaughan (Colorado
State University), Josef W. Zwanziger (Indiana University).
We would be amiss if we did not acknowledge the careful work of our project
editor, Gina J. Linko. Finally, we would like to especially note the contribution of
B. Ramu Ramachandran, Louisiana Tech University, whose work on the end-of-
chapter problems and on the Solutions Manual has been an important part of this
edition.
Keith J. Laidler
John H. Meiser
Bryan C. Sanctuary
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The Nature of Physical
Chemistry and the
Kinetic Theory of Gases
PREVIEW
In each Preview we focus on the highlights of the chapter where R is the gas constant. A gas that obeys this
topics and attempt to draw attention to their importance. equation is called an ideal gas.
As you begin to learn the language of physical chemistry, Experimental observations as embodied in these
pay particular attention to definitions or special terms, laws are important but so too is the development of a
which in this book are printed in boldface or italic type. theoretical explanation for these observations. An
Physical chemistry is the application of the methods important development in this regard is the calculation
of physics to chemical problems. It can be organized of the pressure of a gas from the kinetic-molecular
into thermodynamics, kinetic theory, electrochemistry, theory. The relation of the mean molecular kinetic
quantum mechanics, chemical kinetics, and statistical energy to temperature, namely,
thermodynamics. Basic concepts of physics, including
classical mechanics, are important to these areas. We Ee = shyt (kg = Boltzmann constant)
begin by developing the relation between work and
kinetic energy. Our main interest is in the system and its allows a theoretical derivation of the ideal gas law and
surroundings. of laws found experimentally.
Gases are easier to treat than liquids or solids, so we
Molecular collisions between gas molecules play an
treat gases first. Following are two experimentally important role in many concepts. Collision densities,
derived equations relating to a fixed amount of gas: often called collision numbers, tell us how often
Boyle's Law: PV = constant,, collisions occur in unit volume between like or unlike
(at constant T and n) molecules in unit time. Related to collisions is the idea
of mean free path, which is the average distance gas
V molecules travel between collisions.
Gay-Lussac’s Law: 7 = constant),
Real gases differ in their behavior from ideal gases,
(at constant P and n) and this difference can be expressed using the
compression factor Z = PV/nRT where Z = | if the real
These expressions combine, with the use of Avogadro's
gas behavior is identical to that of an ideal gas. Values of
hypothesis that the amount of substance n (SI unit:
Z above or below unity indicate deviations from ideal
mole) is proportional to the volume at a fixed T and P, to
behavior. Real gases also show critical phenomena and
give the ideal gas law:
liquefaction, phenomena that are impossible for an
PV = nRT ideal gas. Study of critical phenomena, in particular
supercritical fluids, has led to development of industrial between gas particles and in which the ideal volume is
processes as well as analytical techniques. The concept reduced to allow for the actual size of the gas particles,
that there is complete continuity of states in the is an important expression for describing real gases. This
transformation from the gas to the liquid state is equation and others led to a greater understanding of gas
important in the treatment of the condensation of gas. behavior, and also provided the means to predict the
The van der Waals equation, in which the pressure of behavior of chemical processes involving gases.
the ideal gas is modified to account for attractive forces
L
© OBJECTIVES
The purpose of this section is to give a minimum listing m Understand the concept of absolute zero and the use
of knowledge or computational skills that should be of the Kelvin temperature.
mastered from each chapter. This section is not meant to = Develop the mole concept and link it with Avogadro’s
be all inclusive since the true understanding of physical hypothesis.
chemistry should allow the application of the principles
m Clearly define the conditions of the kinetic-molecular
presented to situations and cases not covered here. Some
theory and be able to calculate the pressure of an
instructors may emphasize additional areas of study.
ideal gas from its premises. :
In this chapter and each succeeding chapter, the
student must be able to define and understand all of the Calculate the mean-square speed of molecules.
boldface terms and should be familiar with, as well as Determine the partial pressure and the rate of effusion
able to use, all the key equations at the end of each of gases.
chapter. m Calculate the number of molecular collisions under
After studying this chapter, the student should be given conditions, the related collision diameters, and
able to: the frequency, density, and mean free path.
m Show the relationship between work and force and = Be able to derive the barometric distribution law and
calculate the work under various force conditions. to work through the Maxwell-Boltzmann distribution
m= Calculate kinetic and potential energies. Identify law.
systems and states and be able to determine m Explain and use the compression factor, critical point,
equilibrium conditions. critical temperature, and critical volume, and relate
Calculate the temperature using different fluids. these to a supercritical fluid.
Determine P, V, n, T; or R relationships under = Be able to work the problems related to the various
conditions for Boyle’s law, Gay-Lussac’s (Charles’s) equations of state, including the law of corresponding
law, and the ideal gas law. states and the virial equation.
Humans are exceedingly complex creatures, and they live in a very complicated
universe. In searching for a place in their environment, they have developed a
number of intellectual disciplines through which they have gained some insight into
themselves and their surroundings. They are not content merely to acquire the
means of putting their environment to practical use, but they also have an insatiable
desire to discover the basic principles that govern the behavior of all matter. These
endeavors have led to the development of bodies of knowledge that were formerly
known as natural philosophy, but that are now generally known as science.
1.1 © The Nature of Physical Chemistry

In this book, we are concerned with the branch of science known as physical chem-
istry. Physical chemistry is the application of the methods of physics to chemical
problems. It includes the qualitative and quantitative study, both experimental and
theoretical, of the general principles determining the behavior of matter, particu-
larly the transformation of one substance into another. Although physical chemists
use many of the methods of the physicist, they apply the methods to chemical struc-
tures and chemical processes. Physical chemistry is not so much concerned with the
description of chemical substances and their reactions—this is the concern of or-
ganic and inorganic chemistry—as it is with theoretical principles and with
quantitative problems.
Two approaches are possible in a physicochemical study. In what might be
called a systemic approach, the investigation begins with the very basic constituents
of matter—the fundamental particles—and proceeds conceptually to construct
Microscopic Properties larger systems from them. The adjective microscopic (Greek micros, small) is used
to refer to these tiny constituents. In this way, increasingly complex phenomena can
be interpreted on the basis of the elementary particles and their interactions.
Macroscopic Properties In the second approach, the study starts with investigations of macroscopic ma-
terial (Greek macros, large), such as a sample of liquid or solid that can be easily
observed with the eye. Measurements are made of macroscopic properties such as
pressure, temperature, and volume. In this phenomenological approach, more de-
tailed studies of microscopic behavior are made only insofar as they are needed to
understand the macroscopic behavior in terms of the microscopic.
In the early development of physical chemistry, the more traditional macro-
scopic approach predominated. The development of thermodynamics is a clear
example of this. In the late nineteenth century, a small number of experiments in
physics that were difficult to explain on the basis of classical theory led to a revolu-
tion in thought. Growing out of this development, quantum mechanics, statistical
thermodynamics, and new spectroscopic methods have caused physical chemistry
to take on a more microscopic flavor, particularly throughout the latter part of the
twentieth century.
Physical chemistry encompasses the structure of matter at equilibrium as well as
the processes of chemical change. Its three principal subject areas are thermodynam-
ics, quantum chemistry, and chemical kinetics; other topics, such as electrochemistry,
have aspects that lie in all three of these categories. Thermodynamics, as applied to
chemical problems, is primarily concerned with the position of chemical equilibrium,
with the direction of chemical change, and with the associated changes in energy.
Quantum chemistry theoretically describes bonding at a molecular level. In its exact
3
4 Chapter 1 The Nature of Physical Chemistry and the Kinetic Theory of Gases
treatments, it deals only with the simplest of atomic and molecular systems, but it can
be extended in an approximate way to deal with bonding in much more complex mole-
cular structures. Chemical kinetics is concerned with the rates and mechanisms with
which processes occur as equilibrium is approached.
An intermediate area, known as statistical thermodynamics, links the three
main areas of thermodynamics, quantum chemistry, and kinetics and also, through
computer simulations, provides a basic relationship between the microscopic and
macroscopic worlds. Related to this area is nonequilibrium statistical mechanics,
which is becoming an increasingly important part of modern physical chemistry.
This field includes problems in such areas as the theory of dynamics in liquids, and
light scattering.
1.2 © Some Concepts from Classical Mechanics

We will often calculate the work done or a change in energy when a chemical
process takes place. It is important to know how these are related; therefore, our
study of physical chemistry begins with some fundamental macroscopic principles
in mechanics.
Work
Work can take many forms, but any type of work can be resolved through dimen-
sional analysis as the application of a force through a distance. If a force F (a
vector indicated by boldface type) acts through an infinitesimal distance dl (I is the
position vector), the work is
dw=F-dl Cle)
If the applied force is not in the direction of motion but makes an angle @ with this
direction (as shown in Figure 1.1), the work is the component F cos @ in the direc-
tion of the motion multiplied by the distance traveled, dl:
dw = F cos 6 dl (UE)
Equation 1.2 can then be integrated to determine the work in a single direction. The
force F can also be resolved into three components, F,, F,, F,, one along each of
the three-dimensional axes. For instance, for a constant force F’,, in the X-direction,
w= i Ee dia Fox =X) (xo = initial value of x) Cle}
Several important cases exist where the force does not remain constant, includ-
Hooke’s Law ing gravitation, electrical charges, and springs. As an example, Hooke’s law states
that for an idealized spring
F = Kp xX (1.4)
FIGURE 1.1
Work is the applied force in the
direction of motion multiplied by dl.
1.2 Some Concepts from Classical Mechanics 5
*Hook’s Law: Calibrate a spring where x is the displacement from a position (x) = 0) at which F is initially zero,
balance and weigh masses on and k;, (known as a force constant) relates the displacement to the force. See Fig-
different planets. ure 1.2. The work done on the spring to extend it is found from Eq. 1.3:
O w= i Hig dx = — Hh?
5
(1.5)
0 2
A particle vibrating under the influence of a restoring force that obeys Hooke’s law
Harmonic Oscillator is called a harmonic oscillator. These relationships apply fairly well to vibrational
variations in bond lengths and consequently to the stretching of a chemical bond.
Kinetic and Potential Energy’

Kinetic Energy The energy possessed by a moving body by virtue of its motion is called its kinetic
energy and can be expressed as
Energy: Calculate the kinetic
energy of a bullet.
E, = ymu (1.6)
a
wher(u dl/dt) is the velocity (i.e., the instantaneous rate of change of the posi-
tion vector / with respect to time) and m is the mass. An important relation between
work and kinetic energy for a point mass can be demonstrated by casting Eq. 1.1
into an integral over time:
y t dl t
w=] RO-d=| FO-“ar= | FO -ud (1.7)
ip to dt i)
Substitution of Newton’s second law,
EK = pa = ee (1.8)
dt
where a is the acceleration, yields

ye u
w=] mM udr=m{ udu (1.9)

hy Gi Up
After integration and substitution of the limits if w is in the same direction as du

(cos 6 = 1), the expression becomes, with the definition of kinetic energy (Eq. 1.6),
l
FIGURE 1.2 w= | FQ): dl = 4mu? — dmud = Ey, - Ey, (1.10)

Plot of Hooke’s law for arbitrary
ly : :
k,. The force, F, is plotted against Thus, we find that the difference in kinetic energy between the initial and final
displacement, x, from an equilib-
states of a point body is the work performed in the process.
rium position at x = 0. The force
constant k;, is normally constant Another useful expression is found if we assume that the force is conservative.
only over short ranges and then Since the integral in Eq. 1.10 is a function of / alone, it can be used to define a new
deviates, causing a departure function of / that can be written as
from the straight-line condition
shown. EO) al ab x0) ied)
7
'Some mathematical relationships are found \in Appendix C

*For CD references, insert CD and click on f¢ you wish to study. Locate the desired topic on
the pull-down menu.
Potential Energy This new function E,(/) is the potential energy, which is the energy a body pos-
sesses by virtue of its position.
Energy: Find the potential For the case of a system that obeys Hooke’s law, the potential energy for a mass
BueI gy,ORa-sPong: in position x is usually defined as the work done against a force in moving the mass to
> the position from one at which the potential energy is arbitrarily taken as zero:
E, (arbitrary units) fy = i a i ee i k,x dx = dk Cia)

0
Thus, the potential energy rises parabolically on either side of the equilibrium posi-
ion. See Figure 1.3. There is no naturally defined zero of potential energy. This
means that absolute potential energy values cannot be given but only values that re-
late to an arbitrarily defined zero energy.
An expression similar to Eq. 1.10 but now involving potential energy can be
obtained by substituting Eq. 1.11 into Eq. 1.10:
1
+x w= | F@)-dl=E,,— Ey,= By,— 0
(1.13)
l0
Rearrangement gives
FIGURE 1.3,
Plot of E, = —|
0
F dx = —zkpx® E Po + Ey, = Ey, + Ex, (1.14)
for the case of a system that
obeys Hooke’s law which states that the sum of the potential and kinetic energies, E,, + E,, remains
constant in a transformation. Although Eq. 1.14 was derived for a body moving be-
tween two locations, it is easy to extend the idea to two colliding particles. We then
find that the sum of the kinetic energy of translation of two or more bodies in an
Elastic Collision elastic collision (no energy lost to internal motion of the bodies) is equal to the sum
after impact. This is equivalent to saying that there is no potential energy change of
Energy: Follow E, and E, of the
interaction between the bodies in collision. Expressions such as Eq. 1.14 are known
arrow of an archer.
as conservation laws and are important in the development of kinetic theory.
a
1.3 # Systems, States, and Equilibrium
Physical chemists attempt to define very precisely the object of their study, which
Systems, states, and equilibrium: is called the system. It may be solid, liquid, gaseous, or any combination of these.
Example of open, closed, and The study may be concerned with a large number of individual components that
isolated systems. comprise a macroscopic system. Alternatively, if the study focuses on individual
=) atoms and molecules, a microscopic system is involved. We may summarize by
saying that the system is a particular segment of the world (with definite bound-
aries) on which we focus our attention. Outside the system are the surroundings,
and the system plus the surroundings compose a universe. In an open system there
can be transfer of heat and also material. If no material can pass between the sys-
tem and the surroundings, but there can be transfer of heat, the system is said to
be a closed system. Finally, a system is said to be isolated if neither matter nor
heat is permitted to exchange across the boundary. This could be accomplished by
surrounding the system with an insulating container. These three possibilities are
illustrated in Figure 1.4.
Physical chemists generally concern themselves with measuring the properties
of a system, properties such as pressure, temperature, and volume. These properties
1.4. Thermal Equilibrium 7
Matter Heat Matter Heat Matter Heat

—<—_-— > ~d
Open Closed Isolated

system system system
Surroundings Surroundings Surroundings

FIGURE 1.4
Relationship of heat and matter Boundary permeable Boundary permeable to heat Boundary impermeable
flow in open, closed, and isolated to matter and heat but impermeable to matter to matter and heat
systems. a. b. c.
may be of two types. If the value of the property does not change with the quantity
of matter present (i.e., if it does not change when the system is subdivided), we say
Intensive and Extensive that the property is an intensive property. Examples are pressure, temperature, and
Properties refractive index. If the property does change with the quantity of matter present, the
property is called an extensive property. Volume and mass are extensive. The ratio
of two extensive properties is an intensive property. There is a familiar example of
this; the density of a sample is an intensive quantity obtained by the division of
mass by volume, two extensive properties.
Compare and contrast stable A certain minimum number of properties have to be measured in order to de-
and unstable equilibrium states termine the condition or state of a macroscopic system completely. For a given
of mechanical systems. An amount of material it is then usually possible to write an equation describing the
oscillatory reaction fails to reach state in terms of intensive variables. This equation is known as an equation of state
equilibrium.
and is our attempt to relate empirical data that are summarized in terms of experi-
a mentally defined variables. For example, if our system consists of gas, we normally
could describe its state by specifying properties such as amount of substance, tem-
perature, and pressure. The volume of gas is another property that will change as
temperature and pressure are altered, but this fourth variable is fixed by an equation
of state that connects these four properties. In some cases it is important to specify
the shape or extent of the surface. Therefore, we cannot state unequivocally that a
predetermined number of independent variables will always be sufficient to specify
the state of an arbitrary system. However, if the variables that specify the state of
Equilibrium the system do not change with time, then we say the system is in equilibrium.
Thus, a state of equilibrium exists when there is no change with time in any of the
system’s macroscopic properties.
14 # Thermal Equilibrium
Zeroth Law of Thermodynamics: It is common experience that when two objects at different temperatures are placed
Animation of bodies with the in contact with each other for a long enough period of time, their temperatures will
same temperature at equlibrium. become equal; they are then in equilibrium with respect to temperature. The con-
?
cept of heat as a form of energy enters here. We observe that the flow of heat from
a warmer body serves to increase the temperature of a colder body. However, heat
is not temperature.
We extend the concept of equilibrium by considering two bodies A and B that
are in thermal equilibrium with each other; at the same time an additional body C is
Zeroth Law of in equilibrium with B. Experimentally we find that A and C also are in equilibrium
Thermodynamics with each other. This is a statement of the zeroth law of thermodynamics: Two
8 Chapter 1. The Nature of Physical Chemistry and the Kinetic Theory of Gases
bodies in thermal equilibrium with a third are in equilibrium with each other. This
then leads to a way to measure temperature.
The Concept of Temperature

and Its Measurement
The physiological sensations that we accept as indications of whether an object is
hot or cold cannot serve us quantitatively; they are relative and qualitative. The first
thermometer using the freezing point and boiling point of water as references was
introduced by the Danish astronomer Olaus Rgmer (1644-1710). On the old centi-
Celsius Scale grade scale [Latin centum, hundred; gradus, step; also called the Celsius scale,
named in honor of the Swedish astronomer Anders Celsius (1701—1744)] the freez-
Temperature: Construct a
ing point of water at 1 atmosphere (atm) pressure was fixed at exactly 0 °C, and the
thermometer with a cold and hot
boiling point at exactly 100 °C. We shall see later that the Celsius scale is now de-
reference; Explore different
temperature scales. fined somewhat differently.
The construction of many thermometers is based on the fact that a column of
a mercury changes its length when its temperature is changed. The length of a solid
metal rod or the volume of a gas at constant pressure is also used in some ther-
mometers. Indeed, for any thermometric property, whether a length change is
involved or not, the old centigrade temperature 6 was related to two defined tem-
peratures. In the case of the mercury column, we assign its length the value J,
when it is at thermal equilibrium with boiling water vapor at | atm pressure. The
achievement of equilibrium with melting ice exposed to | atm pressure establishes
the value of /, for this length. Assuming a linear relationship between the tempera-
ture 6 and the thermometric property (length, in this case), and assuming 100
divisions between the fixed marks, allows us to write
eal eekly) (100°) Cigts)

(Lio0 = Io)
Temperature: Use of Eq. 1.15. where / is the length at temperature 0, and /) and /,o9 are the lengths at the freezing
BS
and boiling water temperatures, respectively. Some thermometric properties do not
depend on a length, such as in a quartz thermometer where the resonance frequency
response of quartz crystal is used as the thermometric property. An equation of the
form of Eq. 1.15 still applies, however. Thermometric properties of actual materials
generally deviate from exact linearity, even over short ranges, because of the
atomic or molecular interactions within the specific material, thus reducing the
value of that substance to function as a thermometric material over large tempera-
ture ranges.
1.5 © Pressure and Boyle’s Law

The measurement of pressure, like temperature, is a comparatively recent develop-
ment. Pressure is the force per unit area. Perhaps one of the most familiar forms of
pressure is that exerted by the atmosphere. Atmospheric pressure is often measured
as a difference in height, h, of a mercury column trapped in an inverted tube sus-
pended in a pool of mercury. The pressure is proportional to h, where P = pgh, p is
the density, and g is the acceleration of gravity. The Italian physicist Evangelista
1.5 Pressure and Boyle’s Law 9
Torricellian vacuum Torricelli (1608-1647) used such a device called a barometer. (See Figure 1.5.) In
(The apparently empty the past the standard atmosphere has been defined as the pressure exerted by a col-
volume contains Hg
atoms that give rise
umn of mercury 760 mm high at 0 °C. In SI units,” the standard atmospheric
Pressure of to the vapor pressure pressure (1 atm) is defined as exactly 101 325 Pa, where the abbreviation Pa stands
Hg column of mercury at the for the SI unit of pressure, the pascal (kg m | s ~ = N m ”). In this system,
temperature of the
133.322 Pa is equal to the pressure produced by a column of mercury exactly 1 mil-
measurement.)
Patm
limeter (mm) in height. Since the pascal is inconveniently small for many uses, the
Pool of mercury
unit torr (named after Torricelli) is defined so that 1 atm = 760 Torr exactly. Thus,
the torr is almost exactly equal to | mmHg. (See Problem 1. 7.) Another unit of
pressure commonly in use is the bar: ne p. ~> & Gm Ace a
1 bar= Ht kPa == ().986923 atm

FIGURE 1.5
[door = tz 3 Kh
compared to eee Y es
A barometer. The height, h, of the
mercury column exerts a pressure 1 atm = 101.325kPa. = “]4,0 TeV
at the surface of the mercury pool.
This pressure is exactly counter- Today, | bar is the standard pressure used to report thermodynamic data (Section 2.5).
balanced by the pressure of the On page 8 we implied that the temperature of a gaseous system could be deter-
atmosphere, Pam, on the surface mined through its relationship to pressure and volume. To see how this can be done,
of the mercury pool.
consider the pressure-volume relation at constant temperature. A gas contained
within a closed vessel exerts a force on the walls of the vessel. This force is related
to the pressure P of gas (the force F divided by the wall area A) and is a scalar
quantity; that is, it is independent of direction.
The pressure of a gas contained in a closed vessel may be measured using a
manometer. Two versions are in common use (Figure 1.6). Both consist of a U-tube
filled with a liquid of low volatility (such as mercury or silicone oil). In both, the
top of one leg of the U-tube is attached to the sample in its container. In the closed-
end manometer, the sample pressure is directly proportional to the height difference
of the two columns. In the open-end manometer, the difference in height of the two
FIGURE 1.6 ae are Vacuum

Two types of manometer. In (a),
depicting an open-end manome-
ter, h is added to or subtracted Fyas
from the atmospheric pressure in
order to find the pressure of gas.
In (b), depicting a closed-end
manometer, the height difference
his directly proportional to the
pressure of the sample, pgh,
where p is the density of the Gas h Gas Gas h
manometric liquid. pressure, pressure, pressure,
Fyas> is Fyas: IS Fyas
Pressure: The use of the greater than less than
atmospheric atmospheric
barometer.
pressure pressure
a Fyas = Patm + Pgh

a
Fyas = Patm —pgh Fyas =Pgh
b.
*See Appendix A for a discussion of SI units and the recommendations of the International Union of
Pure and Applied Chemistry.
columns is proportional to the difference in pressure between the sample and the at-
mospheric pressure.
Barometers and manometers fall into a class of pressure measurement devices,
which depend on the measurement of the height of a liquid column. These are used
for only moderate pressures. A second class of devices involves the measurement of
the distortion of an elastic pressure chamber. These devices include Bourdon-tube
gauges for high pressures and diaphragm gauges for more moderate pressures. The
third class of devices is based on electrical sensors. Strain gauges are used for mod-
erate pressures into the vacuum range. For the measurement of still lower vacuum,
Pirani gauges or thermocouple gauges are used down to 10° Torr. Below this pres-
sure more sophisticated gauges are used, such as thermionic ionization gauges, cold
cathode gauges, and Baynard-Alpert ion gauges. Discussion of these devices is
beyond the scope of this book.
EXAMPLE 1.1 Compare the length of a column of mercury to that of a column

of water required to produce a pressure of 1.000 bar. The densities of mercury and
water at 0.00 °C are 13.596 g cm™® and 0.99987 g cm ~, respectively.
Solution The pressure exerted by both liquids is given by P = pgh. Since the
length of both liquids must exert the same pressure, we can set the pressures equal
with the subscripts Hg and w, denoting mercury and water, respectively.
PugSlug = Pw8hw
The height of mercury column required to produce | bar pressure in mm is found
by using what are called unit conversions derived from the definitions. Thus from
the definition: 1 bar = 0.986923 atm, a unit conversion factor may be written as
0.986923 atm bar'.The value of this result is unity. Multiplication by 760 mm
atm' (another unit conversion) merely provides one more unit conversion. Thus
0.986923 atm bar ' X 760 mm atm ' = 750.06 mm bar', or 1 bar = 750.06
mmHg. Substitution of this into the rearranged earlier equation gives
h,, = 750.06 ——~ X 13.596 gcm*

= = 10 199 —ormomoo=—
bar 0.99987 g cm — bar bar
Thus, | bar = 10.199 m water.
In the middle of the seventeenth century, Robert Boyle (1627-1691) and his
assistant Robert Hooke (1635-1703) made many investigations of the relationship
between pressure and volume of a gas. They did not actually discover the law that
Boyle’s Law has come to be called Boyle’s law,° but it was first announced by Boyle in 1662,
and can be expressed as follows:
Ideal gases: Plot isotherms of
The pressure of a fixed amount of gas varies inversely with the volume if
Boyle’s Law.
the temperature is maintained constant.
a
*The law was discovered by the amateur investigator Richard Towneley (1629-1668) and his family
physician Henry Power (1623-1668). The law was communicated to Boyle who with Hooke confirmed
the relationship in numerous experiments. The first publication of the law was in the second edition of
Boyle’s Experiments physico-mechanical, touching the Spring of the Air, which appeared in 1662. Boyle
never claimed to have discovered the law himself, his work being of a more qualitative kind.
1.5 Pressure and Boyle’s Law 11
-ROerT BOYLE (1627—

Boyle did not discover, but confirmed and
publicized, “Boyle’s law,” as he made clear in his own
writings. He was one of the first to apply the inductive
methods that scientists today take for granted. Boyle
almost single-handedly transformed chemistry into a
respectable branch of science. Boyle can be
reasonably regarded as the first physical chemist.
Boyle was a generous and charismatic man with a
wide circle of friends who were devoted to him. He
exerted a powerful influence on the scientific work of
others, including Newton, who was fifteen years his
junior. Boyle’s investigations were carried out in
collaboration with a team of technicians and research
assistants. He was also deeply interested in other
Robert Boyle was born in Lismore Castle, County
matters, such as world religions and languages. He
Waterford, in the south of Ireland. His parents were of was a member, or “adventurer” as it was called, of the
English rather than Irish descent but lived for a period in
Hudson’s Bay Company, in order to learn about the
Ireland. In 1620 his father, Richard Boyle, a successful
effects of low temperatures. He was active in
and wealthy businessman, was made the Earl of Cork. charitable organizations and he became Governor of
Later, after his elder brother had become the Earl of
the New England Company. Funds identified as the
Cork, Robert Boyle was often humorously described as
“Hon. Robert Boyle’s Trust Fund’ are still used to aid
the “Father of Chemistry and Brother of the Earl of Cork.” native peoples in parts of Canada and the West
Boyle inherited a substantial income, and had no need to
Indies.
work for a living. He was privately educated for the most Boyle died on December 31, 1691, and was buried
part. He never attended a university but he developeda in the chancel of the Church of St. Martin’s-in-the-
considerable interest in philosophy and science. Fields in London.
In or about 1655 Boyle lodged in a house on High
Street in Oxford where he carried out many scientific
investigations on combustion, respiration, and the
properties of gases (see Section 1.5), ably assisted by
Robert Hooke (1638-1703), who designed the famous
air pump that was so effective in the study of gases. In References: Marie Boas Hall, Dictionary of Scientific
Biography, 1, 1970, pp. 377-382.
1668 he moved to London where in the Pall Mall
J. B. Conant, “Robert Boyle’s experiments in pneumatics,”
house of his sister Katherine, Lady Ranelagh, he in Harvard Case Histories in Experimental Science (Ed. J. B.
established a laboratory. He worked on scientific Conant), Cambridge: Harvard University Press, 1957.
problems, such as the properties of acids and alkalies K. J. Laidler, The World of Physical Chemistry, New York:
and the purity of salts. After the discovery of Oxford University Press, 1993; this book contains biographies
and further scientific information about many of the scientists
phosphorus in about 1669, Boyle established many of mentioned in this book.
its properties, particularly its reaction with air R. E. W. Maddison, The Life of the Honourable Robert
accompanied by light emission. Boyle, F. R. S., London: Taylor and Francis, 1969.
Mathematically, Boyle’s law can be stated as
P«1/V, L/P eV, P=constant/V, or
PV = constant (valid at constant T and n) (1.16)
A plot of 1/P against V for some of Boyle’s original data is shown in Figure 1.7a.
The advantage of this plot over a P against V plot is that the linear relationship
makes it easier to see deviations from the law. Boyle’s law is surprisingly accurate
5.0x10°
c é
4.0x 10°
Te 3.0x 1074 a
fe o
= S
FIGURE 1.7 hy 20k 10E 2
(a) A plot of 1/P against V for Az
Boyle’s original data. This linear 1.0x 10°74 vi,
plot, passing through the origin,
shows that PV = constant.
(b) Plot of PV = constant at sev-
id, i i 1 eet 1
Os eee ey
eral different constant tempera-
tures. The temperature is greater V/(Arbitrary units) Volume, V
for each higher curve. a. b.
for many gases at moderate pressures. In Figure 1.7(b), we plot P against V for a gas
at several different temperatures. Each curve of PV = constant is a hyperbola, and
since it represents a change at constant temperature, the curve is called an isotherm.
1.6 * Gay-Lussac’s (Charles’s) Law

The French physicist Guillaume Amontons (1663-1705) measured the influence of
temperature on the pressure of a fixed volume of a number of different gases and
predicted that as the air cooled, the pressure should become zero at some low tem-
perature, which he estimated to be —240 °C. He thus anticipated the work of
Jacques Alexandre Charles (1746-1823), who a century later independently derived
the direct proportionality between the volume of a gas and the temperature. Since
Charles never published his work, it was left to the French chemist Joseph Louis
Gay-Lussac (1778-1850), proceeding independently, to make a more careful study
Ideal gases: Plot isobars of using mercury to confine the gas and to report that all gases showed the same de-
Charles’s Law. pendence of V on 6. He developed the idea of an absolute zero of temperature and
calculated its value to be —273 °C. Thus, for a particular value of the temperature 0
a and a fixed volume of gas Vo and 0 °C, we have the linear relation
V = Vo(1 + a0) (1.17)

where a is the cubic expansion coefficient. The modern value of @ is 1/273.15.
Plots of the volume against temperature for several different gases are shown in
Figure 1.8. It can be seen that the curves of the experimentally determined region
can be extrapolated to zero volume where @ is —273.15 °C. This fact immediately
suggests that the addition of 273.15° to the Celsius temperature would serve to de-
fine a new temperature scale T that would not have negative numbers. The
relationship between the two scales is best expressed as
ik 0
aaa
—— SP HAZ AMS (1.18)
:
That is, the value of the absolute temperature (i.e., the temperature divided by its
unit) is obtained simply by adding 273.15 to the value of the Celsius temperature.
1.7. The Ideal Gas Thermometer 13
V/dm®
Extrapolated
FIGURE 1.8 region
A plot of volume against tempera-
ture for argon, nitrogen, and oxy-
gen. The individual curves show
the effect of a change in molar 0
mass for the three gases. In each T/K 0 200 400 600 800 1000 1200
case one kilogram of gas is used
at 1.00 atmosphere. B/°G! =278.115 2100 0 200 400 600 800
On the new scale, 100 °C is therefore 373.15 K. Note that temperature intervals re-
main the same as on the Celsius scale.
Kelvin Temperature This new scale is called the absolute Kelvin temperature scale or the Kelvin
temperature scale, after William Thomson, Lord Kelvin of Largs (1824-1907),
who as will be discussed in Section 3.1 suggested such a scale on the basis of a
thermodynamic engine.
Gay-Lussac’s law may thus be written in a convenient form in terms of the ab-
solute temperature
V«f, V = constant X 7 or
a = constant (valid at constant P and n) (1.19)
The behavior of many gases near atmospheric pressure is approximated quite well
by this law at moderate to high temperatures.
For all gases that obey the three laws just considered, there exists a surface in a
P, V, T diagram that represents the only states (conditions of P, V, and T) of the gas
that may exist. Figure 1.9 shows lines of constant P (isobar) and constant PV
(isotherm) on the smooth surface.
1.7 * The Ideal Gas Thermometer

The work of Gay-Lussac provided an important advance in the development of sci-
ence, but temperature was still somewhat dependent on the working substance used
in its determination. Since molecular interactions are responsible for the nonlinear
Other documents randomly have
different content
the day before he had struck dismay into the mercenary ranks of
their hereditary foes—he need not say he meant the trading class,
whose shameful supremacy had made England unfit to live in. Their
gallant host had plundered the hostile camp of a sum which
represented one of the greatest triumphs ever achieved over the
Philistine. He called upon him, in their name, not to pay this canaille
a farthing in the pound. And he called upon them to drink confusion
to the respectable classes, coupled with the name of their Arch
Decadent!
Everyone rose to his feet to drink the toast, with the exception of
the bankrupt himself, and his brother, who tried to conceal his
disgust under an air of amused tolerance.
Alistair Stuart was conscious of his brother’s real feeling, and
resented it all the more because he was half ashamed of his own
part in the buffoonery. His tone became louder and more insolent as
he gulped down glass after glass of spirits, and called upon one or
other of his guests to keep up the entertainment.
Nobody dared call upon the Secretary of State. They all knew
enough to feel that he was a stranger in the camp, if not a spy, and
only the emphasized indifference of Stuart to his brother’s presence
gave them courage to go on. The presence of this representative of
all that they professed to loathe and despise, looking on with chill
disapproval, dashed their spirits unexpectedly, and even to their own
ears their customary jests took on a hollow sound.
Presently it came to the turn of a youth seated opposite to the Duke.
He was of a pale and sickly countenance, the whiteness of his face
being accentuated by the black locks which he allowed to grow
down to his neck. His tie was a black sash with flowing ends like that
worn by French Art students in the quarter of Batignolles. He did not
appear to be much more than twenty, and answered to the name of
Egerton Vane.
“Who is he?” Trent asked his neighbour.
“The lunatic with the scarf round his neck? That’s a minor poet. I
don’t suppose you have ever come across his works. He publishes
two volumes every year, at his own expense, of course, with about
twenty poems in each. No one ever reads them, except the
provincial reviewers. He has got an album filled with cuttings from
papers like the Pembrokeshire News and the Berwick-on-Tweed
Gazette. ‘A volume of verse from the graceful pen of Mr. Egerton
Vane’—that’s the kind of incense he feeds on. Once he got a puff in
a paper called the Librarian, and carried it about with him for
months. He said to me with tears in his eyes: ‘This is recognition!’”
Everyone in the room seemed to have some literary or artistic
vocation, except Mendes himself. The motive which brought the
South American there remained unguessed by Trent, but it was clear
that he extracted some amusement from his strange associates.
“That other young fool over there is his brother, Wickham Vane,” the
millionaire continued, indicating a boy of eighteen or thereabouts, at
the other end of the table.
“Does he write poetry, too?”
“No, he doesn’t do anything so material as write. He thinks
beautifully about old tapestry.”
Wickham Vane might have been pursuing his peculiar vocation at
that moment from his absorbed expression. But he roused himself
from his abstraction to pay the homage of attention to his elder
brother.
Egerton Vane held a large sheet of paper in his hand, but before
reading from it he prepared his hearers’ minds by a short allocution.
“The poem I am about to read you strikes an entirely new note in
literature, the note of the unreal. It is a ‘Sonnet to a Drawer in a
Japanese Cabinet.’ I have come to the conclusion that all the poets
who have preceded me have been mistaken in thinking that Nature
was poetical. The artificial only is poetical, because only Art can be
artistic. Nature is incapable of symbolism, and the symbol alone is
truly beautiful. All the glorious sins which reveal themselves crudely
and grossly in mere human beings are latent in exquisite suggestion
in the divinely precious works of Art. Even the handicrafts of the
East are steeped in the splendid sensuality of its peoples. In this
poem I have attempted to do justice to the subtle and elusive vice
which clings like the aroma of putrefying rose-leaves to the
workmanship of a Japanese cabinet in my possession.”
The poet proceeded to read:
SONNET
TO A DRAWER IN A JAPANESE CABINET
What shadow of dead secrets, lemon-eyed,

Lurks in thy black recesses, frightful drawer,
Crowned with the Pagan scent of delicate gore
Fresh from the veins of some green suicide?
Behold thy lacquered sins are glorified

In frantic fowls that round thy handle soar,
Mad with obscure desires, like those that tore
Unclean blue Mænads by the Phrygian tide!
And horrors like vermilion rats awake

And crawl about thee, crooning in my ears
Dim, vampire songs of shrivelled souls that ache
With the strange lust for torture-baths of pain;

Sick with the thirst of poison drunk in vain,
And bleeding with the clammy blood of tears.
The new note thus successfully struck in literature was applauded

with a vehemence that concealed some jealousy on the part of the
other poets present. Only Molly Finucane, who was beginning to feel
herself left out in the cold, asked the author impertinently what his
work meant.
“Nothing!” was the rapt reply. “All Art is quite meaningless.”
The Duke of Trent turned to Mendes.
“And is that absurd and disgusting rubbish the sort of thing which
passes for poetry to-day?”
“Not to-day, perhaps, but it will pass for it to-morrow. If Egerton
Vane goes on long enough, I have no doubt he will found a school.
But I have noticed that most young fellows who begin like that end
by going into a monastery.”
The Duke began to see a new usefulness in the institutions which he
had been brought up to regard with aversion.
The Brazilian, who knew the weak spot in most of his fellow-men,
maliciously threw an apple of discord among the company by asking
Egerton Vane across the table what he thought of the poems of
Rowley Drummer.
The quarrel which instantly arose and raged over the merits of this
distinguished writer showed that envy of a rival’s renown may be a
stronger passion than hatred of the middle classes.
The chief apologist for the poet was a man who had recently
achieved a scandalous success with a novel in which he dealt
faithfully with the vices of all his most intimate friends. The terror
inspired by this performance had made him for the moment the
most courted man in London society, and persons like the brothers
Vane followed him about everywhere in the hope of finding
themselves pilloried to fame in Basil Dyke’s next libel.
Dyke, who found his antipathy to the bourgeoisie sensibly
diminished by every cheque which reached him from his publisher,
and who was already meditating desertion from the decadent ranks
in favour of marriage with an heiress, put forward a claim on behalf
of his client which it did not seem easy to refute.
“He has made vice popular in the person of the British soldier,” he
urged. “He has stamped with brazen hoofs upon the Gordons and
the Havelocks and the prayer-meeting heroes of the Victorian Age,
and has called upon the drudging taxpayer to bow down and
worship a swearing, drinking blackguard. His patriotism is nauseous
in itself, I grant, but then he has made it patriotic to break the Ten
Commandments. He has identified Imperialism with immorality.”
“And therefore, I suppose, you would say with Art?” retorted Egerton
Vane, with ill-concealed annoyance. “All Art is immoral, but it does
not follow that all immorality is artistic.”
“Vulgarity is never artistic,” added the thinker about old tapestry,
coming to his brother’s support. “Rowley Drummer has no sense of
the unreal. He sees life in all its blinding vulgarity, and therefore the
better he paints it, the worse is the result.”
Dyke saw that he had gone too far. It is always bad manners to
praise one poet in the hearing of another. He tried to qualify his
praise.
“I do not defend him as an artist,” he explained, “but as a
demagogue. I say that the coarse passion called patriotism, in his
hands, has been turned to a good purpose. After he has taught the
public to acclaim the hooligans of the barrack-room, they cannot
very well flog the hooligans of the street.”
To the Minister, fresh from his legislative essay, this remark sounded
like a challenge. Once more a doubt invaded his mind as to whether
all that he was listening to was sheer ribaldry, or whether there were
not underlying it some serious purpose, or at least some serious
tendency, of which Cabinet Ministers one day might have to take
heed.
Molly Finucane had been feeling bored for some time, and, what was
worse, feeling that her exclusion from the conversation reflected on
her position as the lady of the house. She seized this opportunity to
assert her prerogative.
“Who talks of flogging the hooligans?” she asked, with a good deal
of scorn. “They’ll have to catch ’em first.”
She stopped short, warned by the uneasy looks of the rest that she
had committed herself in some way. Molly did not read the papers,
and so was ignorant of the recent proceedings of the House of
Lords. But she was aware that Lord Alistair’s brother was identified
in some way with the Government, and therefore with the cause of
law and order, and she guessed that her expressions might contain
some element of offence.
There had been a time when Molly would have enjoyed nothing so
much as shocking a Cabinet Minister by telling him across her own
table that her brother was a corner-boy. But for the past year a
great change had come over her disposition, as great as that which
transforms the roystering medical student into the serious family
practitioner. It had not needed the letter from Lord Alistair’s mother
to put before her the idea of becoming Lord Alistair’s wife, nor to
teach her the way in which his friends would take such an alliance.
To become Lady Alistair without at the same time obtaining the
social honours which other Lady Alistairs enjoyed would do little to
satisfy that yearning for other women’s respect which is the torment
appointed for such as Molly Finucane. And there was enough good in
Molly to make her anxious for Alistair’s sake not to be a permanent
blight on his career. It was for his sake as much as for her own that
she had been striving painfully for the last twelve months to acquire
the habitudes of a lady.
The unexpected arrival of the Duke of Trent had caused her a thrill
of pleasurable excitement. To make a good impression on the head
of the family, she felt, would bring her half-way to the goal. Now, at
the thought that she had been so near to disgracing herself, she
could have bitten her tongue.
Molly’s preoccupations were not shared by Alistair, who took it for
granted that his brother had come to reproach him, and resented
what seemed to him an impertinent intrusion. By this time he had
drunk too much to care what he said or did, and the desire was
strong upon him to wreak his bitter feelings on the head of his
favoured elder.
Staggering to his feet, and casting a disdainful look at the silent and
annoyed Duke, he burst out:
“I am a hooligan. I’ve been trying to disguise it ever since I was a
boy, but I’m not going to try any more. I hate your law and order; I
hate your respectability; I hate your civilization. Our forefathers were
thieves and murderers, and I envy them. They lived a jolly life
among the heather and the hills, and they were gentlemen. They
didn’t cringe to cobblers and butchers for votes, and go to church on
Sundays to please their grocer. They swore and drank and diced as
much as they liked, and never asked what the Dissenters thought of
them. I am sick of the strait-waistcoat; I am sick of swallow-tail
coats and prayer-books. Why should I torture myself in the effort to
lead your unnatural life? I protest against it all. Life is one long
persecution of men like me, by men like you. Why can’t you leave
me alone, as I leave you alone? I don’t force you to drink and
gamble, and lead what you are pleased to call an immoral life. Why
do you try to force me to lead a moral one?”
He paused for a moment, and then, as if the overflow of his wrath
had sobered him, went on in a more serious vein:
“What is your ideal? Show me the man you honour, and I will show
you the value of your morality. The hero of to-day is the successful
cheat, the tradesman who has made a million by selling rotten food
to the poor or to your own soldiers in South Africa; the bandit of the
Stock Exchange; the monopolist who has broken the hearts and
ruined the lives of a hundred struggling rivals, and who three
hundred years ago would have been hanged as an engrosser. That is
the man to whom you kneel, for whom all the doors of all the
churches are thrown open, in whose name I am ordered to reform
my ways.”
The speaker seemed to feel the need of pointing his denunciation
with a personal application.
“I am your victim. I am the man whose life is ground out beneath
the Juggernaut wheels of what you call your social system. Why?
Because I cannot become hard and selfish and stupid like your
model. It is monotony that you want; it is originality that you hate.
Go to the tombs of your martyrs—most of them are buried in
Westminster Abbey or St. Paul’s—Goldsmith the bankrupt, Nelson
the adulterer, Pitt the drunkard, Shakespeare the debauchee. Those
are the men whom you are trying to exterminate, and you have
nearly succeeded. I—I had something here, perhaps”—he smote his
forehead with his hand—“and I might have done something if I had
ever had the chance. But you have killed me. All the bright instincts,
all the golden wings that fluttered in the dawn, all the magic
whispers, all the reveries and dreams—they are dead and still and
silent now. Your work is done.”
A slight shiver went round the room and touched even the Cabinet
Minister, who had been more than once on the point of rising and
taking his departure.
Suddenly Alistair Stuart broke into a loud laugh.
“Thank you, my Dishonourable friends—thank you for your support
to-night. You see before you a bankrupt, but a merry one. You will
hear of me again before long. I think of taking a house on the south
side of the river, and turning hooligan. I invite you to become
members of my band. I hope to give some trouble to the authorities.
We are fortunate in having one of them here to-night. I invite you to
drink his health, gentlemen—my brother, the Home Secretary, author
of a Bill to punish the hooligans by flogging. In your name I defy
him, and drink damnation to his Bill!”
The thickness of his speech and the increasing wildness of his
behaviour relieved Lord Alistair’s hearers from the necessity of
treating this as anything but the utterance of an intoxicated man.
But it was clearly necessary to put an end to the scene.
Mendes and the Duke of Trent rose together, but the financier was
the first to speak.
“Gentlemen, it is time we were going. Stuart, sit down! You don’t
know what you are doing!”
He thrust Lord Alistair down into a chair and held him there, while
the others made their hasty farewells and streamed out into the hall.
“I am obliged to you, Mendes,” said the Duke. “Do you think,” he
added in a whisper, “you could get that girl out of the way?”
“It’s her house, I believe, but I’ll try to send her to bed,” was the
answer.
The Brazilian went up to Molly, who sat looking rather frightened at
her end of the table. He said a few words in a low voice which
appeared to produce the right effect. Molly Finucane glanced timidly
at the Duke, and then came towards him with an evident desire to
propitiate.
“I’ll leave him with you, if you like,” she said, “but you won’t find it
much good talking to him to-night, I expect. You’d better come
again in the morning, if it’s any business.”
Trent confined himself to bowing silently, and Mendes accompanied
Miss Finucane out of the room, leaving the brothers together.
Alistair had remained still, with his head resting in his hands, as
though exhausted by his passion. Hearing the door close, he looked
up sullenly.
“Well, what do you want with me?” he asked.
Faithful to his resolve to be gracious, in spite of the provocations he
had received, the Duke made a mild answer.
“I want you to come home, Alistair.”
“This is home.”
“My house is your home,” said James, not unkindly; and, with a tact
of which he was not always capable, he added: “Our mother’s house
is the home of both of us.”
Alistair reddened.
“How is she?” he muttered.
“She is very anxious and unhappy about you. I have promised her to
save you, if you will let me.”
This time the elder brother’s words were not so well chosen. It
always grated on Alistair to be reminded that he was dependent on
James.
“I can’t leave my friends,” he said stubbornly.
Trent thought of the company he had just seen depart, and his
indignation got the better of him.
“Friends!” he repeated. “Friends who have landed you in the
Bankruptcy Court!”
“Well, you didn’t keep me out of it!”
Trent made a strong effort to keep his temper.
“I have seen my solicitor to-day with the object of preventing the
adjudication. Alistair, I will do it, if you will only pull yourself
together, and make it possible for your mother and me to help you. I
will pay your debts once more, though I can ill afford it, and start
you again with a clean sheet, if you will only take advantage of it.
Come! I have got the brougham waiting outside. Why shouldn’t you
get up now, and let me take you straight away with me?”
He tried to speak cheerfully and confidently. But there was no
encouragement in the bleared eyes that looked up at him.
“What! and leave Molly after she’s stuck to me all this time? D’you
think I’m a cad, Trent?”
“You called yourself a hooligan just now.”
Trent regretted the retort the moment it had passed his lips. But it
was too late. Alistair started up angrily.
“And, damn it! I’ll be a hooligan before I will sell the little woman for
a few miserable thousands, like that! Go to the devil, you and your
clean sheet! I’m sorry for the old mater, if she feels it, but I can’t
stand your patronage, and I won’t have your moralizing; so you can
just leave me alone.”
“I will leave you alone!” exclaimed his brother. “God forgive me, I
sometimes wonder what I have done to deserve being cursed with
such a brother as you!”
He turned and strode out of the room, leaving Alistair to sway and
sink down with his head upon the table among the ashes and wine-
stains of the extinguished revel.
CHAPTER VIII
A LEGITIMIST DEMONSTRATION
The carriage which brought the Duchess of Trent and Miss Vanbrugh
to the Legitimist bazaar set them down at the door of a mean-
looking, brick-built schoolroom, over the door of which was a niche
containing the statue of a woman holding a babe in her arms.
This woman was intended for a Jewish peasant, wife of the
carpenter Joseph of Nazareth. This babe was her Divine Son, the
second person of the Christian Triad.
The woman wore an emblem of glory in the form of a crown on her
head. The babe’s head was undecorated. The group was copied
without alteration from the ancient pagan idols of the Great Mother
and her Child, worshipped for countless ages in the Mediterranean
zone.
Beneath the niche four letters were cut. They were the four initials,
A.M.D.G., of the Latin words, Ad majorem Dei gloriam—“To the
greater glory of God.”
It was the motto of the famous Society of Jesus, set up over a
building in which the children of Protestant Churchmen were being
educated. Only the Jesuit motto was not set out in full; it was merely
hinted at by those cryptic letters. This was a touch that Ignatius
Loyola would have admired.
Neither of the two ladies observed the unobtrusive initials, nor, if
they had done so, would they have understood their significance.
But they could scarcely avoid seeing the idol in its niche; and just as
they were stepping out of the carriage a bright little lad, attractively
robed in a white gown with a red vest above, evidently a singing-boy
from the church hard by, passed through the doorway, bowing
reverently to the sacred image as he went up the steps.
The Duchess of Trent was amazed. Her works of charity had never
brought her into this part of the parish, and she had always kept
herself from contact with the religious activities of St. Jermyn’s.
“If that is not Popery, I should like to know what is?” she exclaimed
bluntly to her young friend. “Did you see that boy bowing to the
Virgin Mary? I have no doubt they are taught to pray to her as well.”
This surmise was perfectly just. Such slight control as the
episcopate, or at least the lay judges of the Privy Council, exercised
over the services in St. Jermyn’s Church, appeared to cease
altogether on the threshold of the school. Within that building Dr.
Coles was supreme, and taught what religion he pleased. If it had
suited him to set up an image of Siva for the adoration of his
scholars, or to inculcate the most degrading beliefs of primitive
savagery, no one would have interfered with his discretion. Thus,
while the Vicar maintained some of the forms of Anglican worship in
the parish church, in the schoolroom he had long laid them aside.
The catechism taught to the boys was one prepared by a clerical
secret society, and was carefully contrived to fill the learner’s mind
with hatred for the Protestant heresy, and to turn it in the direction
of Catholic Unity.
A special liturgy, compiled by the same hands, was also provided for
the use of the scholars. In it the Mother of God figured as the
principal, though not the sole, object of worship, the Apostle Peter
taking the second place. Among the prayers, precedence was given
to one for the Patriarch of the West—“Thy servant Leo, that he may
be inspired rightly to define and zealously to defend the faith once
delivered to Thy saints.” After this came petitions on behalf of a
personage discreetly referred to as “the lawful Sovereign of these
realms,” the souls of the dead “now awaiting Thy judgment,” and the
reunion, “under one visible Head on earth,” of all branches of the
Holy Catholic Church. Dr. Coles himself was responsible for a
supplementary prayer in which “our blessed patron, Saint Jermyn,”
was complimented on his influence with the Mother of God, due to
the continence of his life on earth, and implored to use that
influence on behalf of the area for which he was, as it were, the
spiritual County Councillor.
It was a document breathing the spirit of the Dark Ages, when God
figured in men’s minds as a sort of Byzantine Emperor, surrounded
by a court of heavenly chamberlains and eunuchs, each dispensing
favours to his own train of followers, and none incapable of being
bribed.
Miss Vanbrugh, regarding the symbolical sculpture with the
indifference born of ignorance, smiled at her friend’s indignation.
“Let us go in,” she said; “I don’t think it’s so bad inside.”
The whitewashed walls of the room in which they found themselves
offered a curious medley of science and religion, evidencing a painful
struggle in the mind of Dr. Coles between proselytizing zeal and a
desire to earn the grants of an heretical Government. A large crucifix
over the teacher’s desk was flanked by a geological map of Great
Britain, and a glass case containing silk in various stages from the
cocoon to the finished skein. The Ten Commandments on one wall
were faced by the two hemispheres on the other; and an illuminated
calendar of Holy Days was half concealed by a chart depicting
screws, wedges, levers, and other mechanical appliances. The
cloven, or at least the clerical, hoof peeped out in a series of
cartoons illustrative of English history, the scenes chosen being all in
one category—the landing of Augustine, the martyrdom of Edmund,
Thomas à Becket defying Henry II., and Langton, with a formidable
crozier, extorting Magna Charta from King John apparently by the
threat of physical violence, while the barons respectfully looked on.
On this particular occasion the eye was quickly distracted from these
mural decorations by the exhibition beneath. The room, which was
large enough to contain one or two hundred people, was lined round
three sides by stalls loaded with that extraordinary description of
articles which are manufactured specially for sale at bazaars, and in
which the greatest possible uselessness is combined with the
greatest possible fragility. Children’s frocks, which no child could
wear for an hour without damaging them, embroidered tobacco-
pouches sufficient to dismay the most stout-hearted smoker, weird
contrivances of paper and cheap ribbon described as toilet-tidies,
ridiculous pin-cushions, and impossible patchwork quilts formed the
staple of the display. In one corner a lottery was being conducted by
the Rev. Aloysius Grimes, happy in that immunity from the law which
newspaper editors cannot obtain; and pretty little choristers, in their
sacred vestments, were passing to and fro among the ladies doing a
roaring trade in the sale of tickets. But the great attraction of the
afternoon was the theatre, which had been organized in an adjoining
classroom, and in which it was announced that a Miracle Play would
be produced at four o’clock, under the direction of Egerton Vane,
Esq.
As soon as Mr. Grimes caught sight of the Duchess of Trent and her
companion, he handed over the care of the lottery to a young lady
assistant, and hastened forward to greet them. He was just shaking
hands, when a stir in the doorway announced the arrival of Dr.
Coles.
In appearance the Vicar of St. Jermyn’s contrasted very favourably
with his curate. It was easy to see that he was a man of education
and refinement, and his white hairs gave him a certain dignity. His
face was that of a sensualist, but the benevolent smile, which had
become almost stereotyped on his lips, produced an impression of
cordiality and goodness of heart. The Doctor’s career had not been
quite untroubled by the voice of scandal. But any bygone slips on
the part of a saintly man had been forgotten or forgiven. The
reverent murmur which welcomed his appearance among his flock
was a striking testimony to the influence he had secured over those
among whom he worked.
The Rev. Aloysius, breaking away from the two ladies in the middle
of a sentence, without apology, was the first to cast himself on both
knees before his employer, and respectfully kiss a large ring on the
Vicar’s extended forefinger.
“What in the name of goodness does that mean?” the astonished
Duchess asked of Hero.
She spoke loudly enough to be heard by several persons in the
throng, who turned and cast rebuking glances at her. Directly
afterwards she saw a number of well-dressed women advance one
after the other and salute the Vicar of St. Jermyn’s with the same
ceremonial as that observed by Mr. Grimes.
“Are they all mad, or what is it?” the Duchess whispered. “I have
never seen such a thing before in my life, except when I was
abroad, in Roman Catholic society. But even they don’t kneel to their
priests, only to a Bishop.”
Hero blushed guiltily. She was better informed than the Duchess, but
she was not sure that her knowledge might not damage her in her
friend’s eyes.
“Perhaps these people regard Dr. Coles as a Bishop,” she suggested
timidly. “Have you never heard it whispered that he had been
secretly consecrated by—an Armenian Bishop, I think?”
The Duchess stared at her in honest bewilderment.
“How could that be? I don’t understand. Why should an English
clergyman go to Armenia to be consecrated?”
Hero saw that she must make her revelation complete.
“I understand the object was to renew the Apostolical Succession in
the Church of England.”
“It has never been broken,” said the Duchess, with decision. She had
been told so as a girl, and had never given the subject a second
thought. To her devout mind, too candid to be taken in logical
snares, the presence or absence of one or two or three Bishops at
the consecration of another could not seem a matter of real concern.
To attribute to such details the awful consequences they possess for
Catholic minds would have seemed to her to attribute the technical
instincts of a small attorney to the Maker of the sun and stars.
“The Pope of Rome refuses to recognize Anglican Orders, you know,”
Hero explained gently. “The application was made to him the other
day by Lord Bargreave on behalf of a third of the clergy, and he told
them that the English Church had no Bishops, no priests, and no
Sacraments.”
The Duchess flushed to the roots of her hair.
“When I was a girl,” she said sternly, “the Church of England would
have refused to recognize the Pope of Rome. I was brought up to
believe that the Roman communion was a half-pagan, half-political
body, which had corrupted the Gospel with idolatry and superstition,
and forfeited its right to be called a Christian Church.”
It was Hero’s turn to be astonished as she listened to the language
of an extinct generation. Brought up in the age which had witnessed
the triumph of the Ritualist propaganda, it was news to her that the
national Church had ever occupied any attitude but one of envious
imitation or suppliant apology towards that of Rome. And yet Hero
Vanbrugh was a girl who had read a good deal, travelled much, and
used her own powers of observation and reasoning. She had seen
the ignorant priesthoods of Spain and Italy, and their brutish flocks,
the most degraded element in the European population. The sight of
the Rev. Aloysius Grimes cringing to Mike Finigan had roused her
indignation. And yet the spectacle of a great society of Grimeses
cringing to Mike Finigan’s master, in the name of Elizabeth’s and
Cromwell’s countrymen, had scarcely moved her to a passing sigh.
“Times have changed,” she murmured to the Duchess.
And times had. Even the Duchess realized dimly that it had become
unsafe to utter aloud her sentiments of loyalty to the English Church
or to the English Throne in a Church of England schoolroom, while it
had ceased to be unsafe for Dr. Coles to parade openly his treason
to both. His episcopal character was no secret in the theological
colleges from which a steady stream of young men like the Rev.
Aloysius turned their steps to the obscure Lambeth Vicarage in
search of those supernatural powers which they deemed the
neighbouring Archbishop had no power to bestow. In this way the
whole Church was being gradually leavened, so that the time was at
hand when some portion of the mysterious virtue brought from
Armenia would have found its way into all the channels of
ordination, and obstinate Evangelicals would be receiving Armenian
Orders unknown to themselves, and would be working the great
Transubstantiation miracle in which they personally did not believe.
For the sake of achieving this object Dr. Coles had put on one side
the prospect of promotion in the English Church. With abilities
sufficient to have raised him perhaps to the House of Lords, he had
deliberately accepted the part of priest of an obscure parish, content
if his underground revolution was allowed to proceed without
interference. His motives were mixed, perhaps, but great revolutions
are the result of mixed motives, and never of wholly small and base
ones. The Vicar of St. Jermyn’s was blinded to the degrading
character of his methods by the loftiness of his aims. He took the
guilt of fraud and perjury on his conscience, and he did so
contentedly, looking forward to the time when the Church he served
would re-enter the Catholic unity, and the Body of Christ be made
whole.
As soon as he had finished receiving the homage of his peculiar
adherents, the old priest went up to the Duchess of Trent, for whom
he had a warm regard. In spite of the theological gulf that sundered
them, she commanded his sympathy far more than the vain and
hysterical women who grovelled in his confessional, and her simple
and unselfish piety displayed in those good works which all religions
enjoin had won his gratitude and respect. Had he been able to make
a convert of the Duchess he would have felt it as great a triumph as
when the State-appointed Bishop of Linchester, laying aside his
jewelled crozier and mitre, came and knelt in the humble study of
St. Jermyn’s Vicarage to receive them again at the hands of the
“Bishop of Lambeth.”
On her side the Duchess was not blind to the merits of Dr. Coles, his
indefatigable zeal, unworldliness, and kindly temper. They met as
friends meet, seated in different trains, and going in opposite
directions, who exchange a brief word of greeting before they pass
out of each other’s sight.
The Duchess had never referred to the religious aberrations of the
Doctor, but she thought she might safely challenge him on the
subject of loyalty to the Throne.
“I had no idea that you sympathized with the Legitimists,” she
observed.
The Vicar smiled indulgently.
“This bazaar, I suppose you mean? It is more Father Grimes’s doing
than mine. I hold entirely aloof from politics.”
“But you have lent your schoolroom.”
Dr. Coles frowned.
“My schoolroom, as you call it, is a public building,” he said, with a
touch of anger. “I find I am expected to lend it for the purposes of
political meetings, even to the party which almost openly aims at
Disestablishment. I sometimes wonder I don’t receive an application
to lend it for an infidel lecture.”
The Duchess was impressed. Dr. Coles had struck the one note
which brought them into perfect accord, in his reference to infidelity.
In the view of the Duchess this was the one thing worse than
Popery. Her religious scale was made up of five degrees. At the very
bottom came Infidelity, in which term she was disposed to include
the Unitarian denomination and those divines of her own Church
whose Hebrew studies had led them to take different views as to the
authorship of the Old Testament books from those at one time
prevalent. The second head, Popery, covered practically the whole
Christian Church during the ages between the death of Paul and the
conversion of Martin Luther, and two-thirds of existing Christendom.
The third division, under the word Idolatry, embraced the religions of
the rest of mankind, including the stern monotheists of Islam. The
Jews formed a class apart; the Duchess was too good a Conservative
to blame that ancient race severely for their stubbornness in
resisting even a Divine reform; she regarded them as a species of
embryo Christians, whose development had been arrested in the
caterpillar stage. Her fifth division, Protestantism, applied to the
sects dating from the Lutheran revolt, and to stray heretics of the
past, such as the Socialist Lollards and the freethinking Albigeois,
who possessed the merit of having been persecuted by Rome.
Among these, of course, she distinguished between the converted
Christian and the much larger class of sinners for whom she wished
to take for granted a death-bed repentance.
It was not an unimportant matter that the Duchess of Trent should
have held these views. Money is always important, and the Duchess
was one of a very large moneyed class who were always ready to
open their purses on behalf of their favourite propaganda. The
infidel and the sinner were supposed to be reached by the ordinary
machinery of the Church, and the Papist and the Jew had been
wellnigh abandoned as hopeless, though a few Englishmen of the
lower class still prowled through countries like Spain and Portugal,
distributing Protestant tracts and increasing the dislike felt for their
nation. But the great field for missionary effort, of course, was that
section of mankind labelled idolaters or heathen. In the spirit of the
hymn which singles out the inoffensive Buddhists of Ceylon to brand
them with the epithet vile, the good Duchess firmly believed that to
thrust, not merely the theology, but the morals, social customs,
marriage institutions, language, manners, and even clothing of her
own age and country upon all the peoples of the earth was a Divine
injunction to be neglected at her peril.
This generous zeal had long been encouraged by the statesmen of
the Raj, who saw its possessions widened without the expense of
arms. The British Empire resembles no other that has ever existed in
having come into existence unconsciously. England has sent forth
her outlaws on the shores of distant continents, and they have come
back soldiers for her. Her merchants have gone forth seeking
merchandise, and realms Alexander sighed for have fallen like ripe
fruit into their hands. Her missionaries have Anglicized where they
should have Christianized; the bigoted worshippers of Allah and
Vishnu imitate the language of Macaulay, and every new church in
Africa gives a new cotton-mill to Lancashire.
Dr. Coles had a more personal argument in store for the Duchess of
Trent.
“Surely you cannot be very bigoted against the Legitimists,” he
urged. “I thought that all the old Scotch families were Jacobites at
heart. And Lord Alistair Stuart is a member of the Guild.”
“I have heard my mistress, the Queen, say: ‘I am the greatest
Jacobite of them all,’” the Duchess responded. “But I don’t think she
ever expected to hear of real Jacobites in the twentieth century. I
don’t take your friends very seriously, Dr. Coles, and I dare say my
son doesn’t either.”
Before the discussion could be carried further Alistair himself came
into view. His mother watched him anxiously, half afraid of seeing
him accord the same homage to Dr. Coles as the others. But
whether because he was wanting in reverence for Armenia, or
because he was ashamed to show greater respect to a man than to
his own mother, Stuart contented himself with shaking hands with
the priest, after he had previously greeted his parent.
He was surprised at first to see her at such a function. But the
diplomacy of the Duchess was very transparent. She at once turned
to Hero, and pronounced the formula which entitles two people in
English society to know of each other’s existence.
It was the first time Alistair had seen Miss Vanbrugh, but not the
first time he had heard her name. The eyes of society are very keen
where a man like the Duke of Trent and Colonsay is concerned, and
its whispering-gallery is very wide. Although the Duke himself had
never given any significance to his intercourse with Hero, the correct
significance had already been given to it by others, and the rumour
had reached Lord Alistair. For him the girl who stood before him was
the girl who was on the point of becoming his brother’s betrothed.
He raised his eyes to her face, and when he saw that picture of
calm, sweet maidenhood, with all the bloom of youth and purity
upon it, and those eyes radiant with high and happy thoughts, and
when he recalled that other face he had just quitted, with the paint
peeling off under the haggard eyes, and the cracked lips set in a
querulous scowl because he had not dared to bring her into the
company of reputable women, and when he compared his own lot,
cast with that unhappy creature, with the life that lay before his
brother, blest in so dear a wife, then his heart failed him, and he had
to turn away his eyes to hide the unexpected smart.
On her part Hero was not much less moved. She saw standing
before her the figure around which her imagination had already
woven its romance, and he was handsomer than the hero of her
romance. The gracefully-knit form, with its statuesque neck and
curling dark hair, breathed the very spirit of the lays of Oisin. The
swish of the heather was still in his elastic tread, the sunlight of the
rain-washed Hebrides was in his glance. She seemed to see him in
his kilt and plaid, the eagle’s feather nodding in his bonnet, and the
claymore by his side, a young chieftain of the glens, starting at
daybreak from his bed among the fern, and setting forth perhaps to
woo a maiden like herself with the immemorial charms of song and
dance. In the strait garb of the decorous capital he seemed to her
like a shorn Samson, and she thought of violets fading in a city
garret, and skylarks caged in a dark cellar beating their wings in
want of light and air.
She, also, drew her comparison, and the cold and perfect courtier of
Colonsay House suffered by it. For the first time she felt in its full
strength that instinct of self-sacrifice which lies at the core of every
noble nature. The task which Stuart’s mother had offered to her, and
in which she had only taken a sentimental interest, now became a
fascination. The longing to save this glorious soul, fallen among
weeds and briars, to lift it up and wipe away its stains, and set it on
its true path again, overcame her like the touch of love; the touch of
love overcame her like the longing to save, and her hand trembled in
Alistair Stuart’s.
The two Vanes sidled up, anxious to be recognized by their chief.
“So glad you have turned up, Stuart,” bleated the elder. “It’s quite a
demonstration, isn’t it?”
“Yes,” Wickham echoed, “it is a blow. I think we are striking a blow.”
He meant at the hated middle classes. It was the only kind of a blow
he was ever likely to strike against that or any other enemy.
Stuart heard them with impatience. Somehow the presence of Hero
made the two brothers look tawdry and ridiculous with their
decadent cant, their untidy hair, and their silly, outlandish neckties.
He answered with irony:
“No doubt the middle classes will be frightened when they hear of
this bazaar. But you must see that it gets into the papers, otherwise
the effect will be lost. Are there any reporters here?”
The brothers looked around a little nervously.
“I hope so,” said Egerton, whose vanity was slightly greater than his
cowardice.
“It might vulgarize the thing,” suggested Wickham whose cowardice
was slightly greater than his vanity.
Stuart understood their fears, and played on them by way of
distraction from his secret emotion.
“I expect the place is crammed with detectives,” he observed. “I
fancied I saw one or two suspicious-looking fellows with notebooks
as I came in.”
Hero grasped the situation, and smiled.
“No; do you think so?” exclaimed the elder Vane in a tone of
exultation, tempered by alarm. “But surely there is nothing they can
take hold of—nothing illegal, I mean—in a bazaar?”
“They may shadow us after this, though,” muttered the junior, in
whom alarm had got the better of exultation.
“They may treat the bazaar as evidence of a conspiracy,” Stuart
suggested cheerfully. “But here comes St. Maur; you had better ask
him.”
He turned, and led Hero away through the crowd, to escape from
the person he had indicated, leaving the brothers in a state of cruel
apprehension.
But Mr. St. Maur was not to be shaken off so easily. This gentleman,
who had spelt his name “Maher” in his native city of “Dahblin” (as he
was accustomed to pronounce it), was the son of a decent butter-
merchant, who had put him to the Bar. Coming over to the Temple,
in accordance with old custom to keep his terms, the ambitious
youth was surprised and charmed to find that his membership of the
Roman Church, which had stood somewhat in his light in the society
of the Irish capital, was here a fashionable distinction. To drink the
Roman Pontiff’s health before that of the British Sovereign appeared
to be in some mysterious way a passport to Court favour, and a
Roman missionary had just been given precedence over the heads of
the English Church. The policy of the Primrose League had been
adapted to the purposes of proselytism, and a club had been
founded in the West End in which the middle-class aspirant could
enjoy the privilege of lunching in the same room as a Roman
Cabinet Minister and receiving the Times fresh from the hands of a
Roman Duke. Unfortunately the Duke and the Cabinet Minister failed
to play their parts with sufficient zeal, or else there were not enough
of them to go around, and St. Bridget’s Club gradually sunk from
depth to depth till not merely Protestants, but Jews, profaned its
portals, and it became a refuge for all the suspicious characters
whom other clubs refused.
Young Maher was not long in deciding to forsake the Irish Bar for
the English, and a slight alteration in the spelling of his name
enabled him to pose as an offshoot of one of the greatest families in
Britain. The difficulty of an accent which clove obstinately to his
tongue was met by a well-constructed legend of an Irish branch of
the family in question, supposed to have settled in the Emerald Isle
about the time of Strongbow. On the strength of this genealogy,
which would have done credit to the Heralds’ College in its best
remunerated moments, Mr. St. Maur was in the habit of referring to
a nobleman of lofty rank as “the head of our house,” thereby causing
intolerable anguish to his friends, the Vanes, who were only
nephews of a baronet. Unfortunately they were prevented from
questioning the genuineness of St. Maur’s pedigree, inasmuch as
they had laid every stress upon it in introducing him to their
acquaintance. But they had an uneasy sense that the Irishman was
an impostor who had beaten them by mere bluff.
On his part the barrister having, as he conceived, surpassed the
Vanes, was seeking for loftier heights to scale. As soon as he met
Lord Alistair Stuart in the brothers’ flat he promptly marked him out
for attack. Undaunted by Stuart’s evident dislike for him, the
Irishman persistently forced himself on his notice. With this object
he had thrown himself heart and soul into the Legitimist cause, as
he would have thrown himself into the Independent Labour Party
the day after if the leaders of that movement had been members of
the peerage.
Having come to the bazaar chiefly in order to push his acquaintance
with Lord Alistair, Mr. St. Maur was not the man to be balked of his
prey.
“Grand success, this, isn’t it, Stuart?” he bawled out from afar, as he
hustled his way through the throng.
Much as Stuart disliked his follower, he failed to give him credit for
the naked singleness of his aims. Had he fully understood the
Irishman’s character, he would have got rid of him before this by the
easy expedient of introducing him to his brother. Once anchored to
the coat-tails of a Duke, St. Maur would have left a mere younger
brother severely alone. As it was, Lord Alistair saw no way of
repelling the intruder except by a harshness which was not in his
nature.
Mr. St. Maur shook hands effusively, and then, finding he was not
going to be introduced to Lord Alistair’s companion, began enlarging
on the prospects of the movement.
“I consider this affair will launch us as a serious party,” he declared.
“The public will begin to reckon with us. It will soon be time to think
of a Parliamentary candidature. What do you say, Stuart?”
Alistair shrugged his shoulders.
“I should think you would get about ten votes in any constituency in
England.”
“Ah, but what about Scotland? There is a feeling up there that might
be appealed to. If a man like yourself, now, a member of an old
Highland family, were to stand in your own part of the country, don’t
you think the clansmen would rally round you?”
“You forget that I should have my brother’s influence dead against
me. He is a member of the Government.”
“He would have to disavow you officially, of course. But privately,
you know? Don’t you think the Duke might be brought to show some
sympathy for the movement?”
“He would simply laugh at it, I expect,” said Stuart.
“The Duke of Gloucester does not laugh at it,” returned the other.
Alistair’s face darkened at the name, and he cast down his eyes.
“How do you know that?” he asked.
St. Maur swelled with importance.
“I happen to have private information that he watches the
proceedings of the Guild with the closest attention. He has
everything that appears in the press about us sent him by a press-
cutting agency.”
“I wish I had known that before,” said Alistair. And, turning to Hero,
he explained: “I have let them have an autograph letter of the
Prince’s to sell at one of the stalls.”
The absurdity of this did not strike Hero so much as its ingratitude.
“A letter from the Prince to you, do you mean?” she asked, with an
accent of reproach.
“Yes; I used to know him very well when we were boys. I came
across it the other day among some old papers. But I shouldn’t like
him to hear that I had let it be sold.”
A purpose had swiftly formed in Hero’s mind.
“Whereabouts is the stall?” she inquired.
“Over here.”
Turning his back on Mr. St. Maur with unwonted rudeness, he
conducted Hero to a stall presided over by a pretty, overdressed little
woman, who had been persuaded by Mr. Grimes in the confessional
that she would thus atone for certain errors to which pretty,
overdressed little women are prone. Prince Herbert’s autograph had
been entrusted to her for sale, and by good luck it had not been
disposed of when the two came up.
“What is the price of this letter?” Miss Vanbrugh asked quickly.
“One guinea,” the stallkeeper simpered. “It is from His Royal
Highness the Duke of Gloucester to Lord Alistair Stuart,” she added
in ignorance of who stood before her.
“Let me buy it, and give it to you!” cried Alistair, guessing Hero’s
design.
She took up the letter. It was a short schoolboy’s note, and
contained a misspelt word.
“Dear Alistair:
“I cannot meet you to-morrow, as the Crown Prince of
Austria is coming, but I will go out fishing on Saturday if
you like. Come over here at ten o’clock—mind, be
punctual.
“Yours affectionately,
“Herbert.
“P.S.—Sorry to break my promise, but they made me.
Mind, bring your fishing-rod.”
Hero handed the letter to her companion.
“I would rather you let me buy it, and give it back to you,” she said.
She handed the money to the lady of the stall, who was looking
considerably astonished.
Alistair understood the delicate rebuke. His glance took in the
contents of the friendly, boyish note afresh, and he felt ashamed
that he had parted with it.
“I am very grateful to you, Miss Vanbrugh, believe me,” he said
earnestly, as he slipped the letter into his pocket. “I ought not to
have let it go into strange hands. But I hope I needn’t count you as
a stranger. You are often at Colonsay House, aren’t you?”
“I have never met you there,” said Hero pointedly.
And Alistair was silent.
The Miracle Play was a great success, though not, perhaps, in the
way anticipated by Dr. Coles.
The Vicar had understood that the text of the Ober-Ammergau
performance was to furnish the basis of a version only slightly
modified by Mr. Egerton Vane. But Mr. Vane, being deeply imbued
with the spirit of Maeterlinck, had allowed his adaptation to become
tinctured to an unforeseen extent by the vein of symbolism peculiar
to the work of the Belgian master. The orthodox Christian
interpretation being repugnant to his feelings as a Pagan, he had,
moreover, boldly replaced it by something more congenial to his own
sympathies.
The result was somewhat as though a conscientious Buddhist should
rewrite “Paradise Lost,” endeavouring to make it illustrate the
doctrine of metempsychosis.
In the opening scene Mary was introduced as the Spirit of Form,
receiving the Annunciation from the Angel Gabriel as the
representative of Creative Genius. The dialogue, which was
fortunately unintelligible to nine-tenths of the audience, turned on
the sterility of the Jewish nation in the department of the plastic
arts. Mary was informed that her Son would remove the prohibition
contained in the Second Commandment, thereby opening the way
for the Christian school of statuary and painting.
The whole of the sacred narrative was dealt with from the same
standpoint. The Wise Men were presented as the exponents of the
three arts of Poetry, Music, and Painting, whose respective merits
were discussed at some length. The dispute of the child Christ in the
Temple was made to turn on Keats’s famous identification of Truth
with Beauty. Satan, in the scene of the Temptation, appeared as the
genius of Utilitarianism and the middle classes, urging the Christ to
abandon the principle of Art for Art’s sake. Towards the end of the
drama Byron’s jest about Barabbas was almost literally incorporated,
Barabbas being designed as a type of commercial success in
literature—a Jewish Tennyson or Ruskin.
Every allusion to the Jews as a people was barbed with the bitterest
malignity. The Semitic spirit was branded, with some historical
confusion, as that of Philistinism par excellence; and Isaiah and
other prophets were ingeniously represented as having fallen
martyrs to their literary excellence rather than to their reforming
energy.
The allegory was so vague and the dialogue so obscure that most of
those present entirely failed to grasp the enormity of the author’s
transgression. But it was otherwise with Dr. Coles. The Armenian
proselyte was a learned and thorough-going medievalist, and he had
taken it for granted that medieval traditions would be strictly
adhered to. He had left the work of superintending the rehearsals to
his curate, never deeming that Mr. Grimes was capable of betraying
the trust. Nor was he, had he been sufficiently intelligent to perceive
that he was being made a cat’s-paw by his pagan librettist. The
actors in the piece, being the choir-boys, were even less capable of
judging of the drift of the performance.
The deeply mortified Vicar restrained his wrath till the moment when
the High-Priest Caiaphas came upon the scene in the thinly-
disguised character of the proprietor of a morning paper with an
enormous circulation, when it became impossible to mistake the
dramatist’s intentions. Rising from his seat in the front row of the
audience, Dr. Coles gave a peremptory order for the curtain to be let
down, and the thoroughly mystified spectators seized the
opportunity to escape.

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Physical chemistry Vol III Gurtu

Atkins Physical Chemistry 11th Edition Peter Atkins

Physical Chemistry 3rd Edition Robert G. Mortimer

Sita Daughter of the Earth Saraswati Nagpal

Handbook of Neurochemistry and Molecular Neurobiology

Musicology The Key Concepts Routledge Key Guides David

The Market for Liberty 40th Anniversary Facsimile

Principles Digital Communication System Computer

Atomic Atomic Atomic Atomic

Actinium* Ac 89 (227.028) Neodymium Nd 60 144.24(3)

*The elements marked with an asterisk have no stable isotopes.

SS UE Poca ey bra ala og82

EO tales tel GIV\ Bal: Sales

Physical Chemistry, Fourth Edition © 2003 Brooks/Cole, Cengage Learning

Cover image: © Greene, Dickinson, and Sadeghpour and

Ludwig Boltzmann, page 788: AIP Emilio Segre Visual

Agnes Pockels, page 953: Reproduced courtesy of the

Printed in the United States of America

Preface xii Equations of State 36

aco) The Kinetic-Molecular Theory of Ideal 2.5 Thermochemistry 62

Changes of State of Aggregation 109 — Ideal Gases 110

6.2 One-Component Systems 228 7.9 Theories of lons in Solution 296

6.7 Crystal Solubility: The Krafft Boundary and Electrochemical Cells oS

92 Rate of Reaction 363 10.6 Photochemical Reactions 437

9.4 Analysis of Kinetic Results 367 10.7 Radiation-Chemical Reactions 443

Method of Integration 368 Half-Life 371 Differential 10.8 Explosions 445

Flow Methods 374 Pulse Methods 376 10.9 Catalysis 449

Oy The Arrhenius Equation 380 10.10 Reactions in Solution: Some Special

9.9 The Preexponential Factor 388 10211 Mechanisms of Polymerization in

9.10 Reactions in Solution 396 10.12 Kinetics of Polymerization 465

10.3 Rate Equations for Composite

10.5 Free-Radical Reactions 431 2 Bohr’s Atomic Theory 509

11.3 The Foundations of Quantum 12.2 The Hydrogen Molecule 583

The Principal Quantum Number n 545 — Angular

Raman Spectra 687 14.12 Mass Spectrometry 775

Appendix: Symmetry Species Corresponding

Some Modern Applications Biography: Ludwig Boltzmann 788

14.7 Electron Magnetic Resonance (EMR) 760

Appendix A Units, Quantities, and

aos Viscosity 968

Changes in This Edition

Organization and Flexibility

A. Chapters 1-6: General properties of gases, liquids, and solutions; ther-

Units and Symbols

Edmund Tisko, University of Nebraska

Segue dese sa rn, Na: Ce pe

Thi - ‘Ai. ML As eee wR,1h Ee) 4h

1.1 © The Nature of Physical Chemistry

1.2 © Some Concepts from Classical Mechanics

w= i Ee dia Fox =X) (xo = initial value of x) Cle}

Kinetic and Potential Energy’

Substitution of Newton’s second law,

where a is the acceleration, yields

w=] mM udr=m{ udu (1.9)

After integration and substitution of the limits if w is in the same direction as du

FIGURE 1.2 w= | FQ): dl = 4mu? — dmud = Ey, - Ey, (1.10)