PHYSICS AND CHEMISTRY OF THE ORGANIC SOLID STATEPDF电子书下载

1．Thermodynamics of crystals＆by Edgar F．Westrum,Jr．,and John P．McCullough 1

Ⅰ．Introduction 3

Ⅱ．General Principles 4

1．Classical Thermodynamics 4

2．Statistical Thermodynamics 12

Ⅲ．Experimental Measurements 15

1．Determination of Thermal Properties by Calorimetric Methods 15

2．Determination of Thermodynamic Properties by Nonealori-metric Methods 35

Ⅳ．Thermodynamic Properties of Crystals 40

1．Experimental Results 40

2．Interpretation and Correlation of Properties 56

Ⅴ．Phase Behavior of Pure Substances 73

1．Polymorphism 73

2．Phenomenological Classifications of Transitions 76

3．Order-Disorder Transitions 85

4．Transitions to the Plastically Crystalline State 89

5．Transitions to the Vitreous State 102

6．Transitions to the Liquid State 103

7．Transitions to the Vapor State 107

8．Electronic and Magnetic Transitions 117

9．Ferroelectric Transitions 121

Ⅵ．Thermodynamic Properties of Free Radicals in Organic Crystals 128

Ⅶ．Thermodynamics of Mixtures 130

1．Organic Solid Solutions 130

2．Clathrates 133

Ⅷ Appendix:Summary of Thermodynamic Data Available for Organic Crystals 135

Ⅸ．References 156

2．Definition and attainment of high purity of organic compounds＆by Gilbert J．Sloan 179

Ⅰ．Introduction 180

Ⅱ．The Determination of Purity 181

1．General Considerations 181

2．Fusion Curves 182

3．Phase Solubility Analysis 189

4．Difference Methods 191

Ⅲ．Zone Refining and Related Techniques 193

1．Theory 193

2．Methods and Results 200

Ⅳ．Countercurrent Distribution 207

1．Introduction 207

2．Theory and General Methods 207

3．Techniques,Apparatus,and Results 209

Ⅴ．Chromatography 210

1．Introduction 210

2．Methods 211

3．Experimental Procedures and Apparatus 211

Ⅵ．Sublimation 215

1．Vapor Zone Refining 215

2．Gradient Sublimation 215

3．Microfractor 216

Ⅶ．References 217

3．Crystal growth＆by G．F．Reynolds 223

Ⅰ．Introduction 224

1．Preliminary Remarks 224

2．Saturation,Supersaturation,Metastable Supersaturation,and Labile Supersaturation 225

Ⅱ．Theory of Crystal Growth:An Introduction 227

1．The Theory of Growth of Perfect Crystals 227

2．The Theory of Growth of Imperfect Crystals 230

Ⅲ．Growth from Solution 242

1．General Considerations 243

2．Preparation of Seed Crystals 245

3．Growth by Cooling 246

4．Growth by Evaporation 249

5．Growth by the Temperature-Difierence Method 254

6．Other Solution Methods 258

Ⅳ．Growth from the Vapor 258

1．General Considerations 259

2．Method a 260

3．Method b 261

4．Method c 264

Ⅴ．Growth from the Melt 266

1．General Considerations 266

2．Bridgman-Stockbarger Method 267

3．Stober Method 272

4．Nacken-Kyropoulos Method 274

5．Crystal Pulling 276

6．Zone Melting Techniques 278

Ⅵ．Special Methods of Growth 281

1．Growth in the Solid State 281

2．Growth through Chemical Change 282

3．Growth through High Pressure and Temperature 283

Ⅶ．References 284

4．Thermal reactions of organic solids＆by H．Morawetz 287

Ⅰ．Introduction 287

Ⅱ．Some Characteristics of Reactions of Inorganic Solids 288

Ⅲ．Special Factors to be Considered with Organic Solid Reagents 291

Ⅳ．Isomerizations 294

Ⅴ．Polycondensations 297

Ⅵ．Chain Reactions 300

1．Decomposition and Isomerization Chain Reactions 300

2．Polymerization Chain Reactions 302

Ⅶ．Szilard-Chalmers Reactions 311

Ⅷ．Reversible Solid-Gas Equilibria 313

Ⅸ．Organic Explosives 316

Ⅹ．Reactions in Solid Polymers 318

1．Depolymerization 318

2．Cross-Linking 320

3．Reactions of Solid Polymers with Small Molecules 322

4．Dccomposition of Small Molecules in a Polymer Matrix 324

Ⅺ．References 324

5．The photochemistry of the organic solid state＆by Hugh S．A．Gilmour 329

Ⅰ．Introduction 330

Ⅱ．Unimolecular Reactions 331

1．Phototropy:Reversible Photoisomerizations 331

2．Irreversible Photoisomerizations 335

3．Free-Radical Formation 336

4．Four-Center Reactions 340

5．Unstable Intermediate Redox States 341

6．Triplet States 341

7．Photoanisotropy 343

Ⅲ．Bimolecular Reactions 345

1．Introduction 345

2．The Triplet State in a Reactive Matrix 345

3．States Intermediate Between Solid and Liquid 346

4．The Formation of Substituted Cyclobutane 347

5．The Addition of Oxygen 351

Ⅳ．Photoelectric Effects 353

Ⅴ．Dyes and Textile Polymers 354

1．Introduction 354

2．Dye Stability 354

3．The Photochemical Tendering of Fabrics 358

4．Photochemical Bond-Forming and Bond-Breaking Reactions in Monomers and Polymers 360

5．The Photochemistry of Elastomers 362

Ⅵ．Diazo Compounds 363

Ⅶ．Energy Transfer 363

Ⅷ．References 363

6．Crystal form and crystal structure＆by P．Hartman 369

Ⅰ．Introduction 370

1．Crystal Form 370

2．Crystal Structure 373

Ⅱ．Form and Structure 377

1．Geometrical Relations 377

2．Structural Relations 380

3．Thermodynamic Relations 395

4．Polar Crystals 397

Ⅲ．Habit Change 398

1．By Change of Supersaturation 398

2．By Change of Solvent 399

3．By Addition of Impurities 400

4．By Differences in Growth Process 402

Ⅳ．Information about Crystal Structure from Morphology 404

Ⅴ．References 407

7．Structure of surfaces＆by W．J．Dunning 411

Ⅰ．Introduction 412

Ⅱ．Thermodynamics of Surfaces 413

1．Definitions 413

2．Wulff＇s Theorem 414

3．Surface Stress 415

Ⅲ．Molecular Theory of Surfaces 415

1．Binding Energies of Molecules 415

2．Estimation of Surface Energy 417

3．Surfaces in the Equilibrium Shape 418

4．Wulff＇s Rule and the Gibbs-Thomson Equation 418

Ⅳ．Statistical Mechanics of Surfaces 421

1．Dependence of Line Tension on Orientation 421

2．Equilibrium Shape of a Two-Dimensional Crystal 422

3．Dependence of Surface Tension on Orientation 424

4．Equilibrium Shape of a Crystal 426

Ⅴ．Experimental 427

1．Direct Determination of the Surface Tension 427

2．Experimental Investigation of Crystal Form in Relation to Surface Structure 434

3．Growth Surfaces 439

4．Etched Surfaces 445

5．Cleavage Surfaces 447

6．Polymeric Surfaces 450

Ⅵ．References 456

8．The crystallization of long-chain polymers＆by H．D．Keith 461

Ⅰ．Introduction 462

1．Objective and Approach 462

2．Historical Outline 463

Ⅱ．Molecular Structure and its Organization in the Crystalline State 466

1．Classification of Molecular Structures 466

2．The Structure of Polymer Molecules in Relation to their Ability to Crystallize 469

3．Some Representative Crystal Structures 480

Ⅲ．The Morphology of Solution-Grown Crystals 491

1．Superficial Characteristics 491

2．Finer Details of Crystalline Morphology and the Geometry of Molecular Folding 497

3．Theories of the Formation of Chain-Folded Lamellae 505

Ⅳ．The Morphology of Polymers Crystallized from the Melt 513

1．Spherulitic Crystallization 513

2．Molecular Orientations in Polymer Spherulites 516

3．The Nature of the Radial Fibirls 522

4．The Growth and Over-all Structure of the Spherulites 525

5．Mechanisms of Crystallization in Bulk Polymers 530

Ⅴ．References 539

9．Plastic crystals＆by John Geldart Aston 543

Ⅰ．Introduction 543

Ⅱ．Mechanical Mobility and＂Viscosity＂of Plastic Crystals 544

Ⅲ．Lattice Parameters and X-Ray Reflection from Plastic Crystals 548

Ⅳ．Dielectric Constant of Plastic Crystals 551

Ⅴ．Calorimetric Studies of Molecular Rotation 555

Ⅵ．The Effect of Mobility of Plastic Crystals on the Nuclear Magnetic Resonance Absorption Line 562

Ⅶ．Solid Solutions Involving Plastic Crystals 571

Ⅷ．Mobility of Absorbed and Adsorbed Spherical Molecules 577

Ⅸ．Theory of Phase Changes in Plastic Crystals 580

Ⅹ．Hindered Rotation in Solids．Concluding Remarks 581

Ⅺ．References 582

10．Visible and ultraviolet absorption by molecular crystals＆by D．P．Craig and S．H．Walmsley 585

Ⅰ．Theoretical 586

1．Introduction 586

2．Spectroscopic Preliminaries 589

3．The Exciton Theory 591

4．The Energies of Crystal States to the First Order 602

5．Higher Approximations 610

6．The Influence of Molecular Vibrations 618

Ⅱ．Experimental 625

1．Methods of Measurement of Crystal Spectra 625

2．Results 631

Ⅲ．Conclusion 645

Appendix 646

Ⅳ．References 653

11．Infrared spectra of molecular crystals＆by David A．Dows 657

Ⅰ．Introduction 658

Ⅱ．Theory 660

1．Vibrations and Spectra 660

2．The Interaction Potential 676

Ⅲ．Methods of Study of Vibrational Spectra of Crystals 681

1．Apparatus and Samples 681

2．Line Shapes,Intensities,and Reflection 684

3．Mixed-Crystal and Matrix Methods 685

Ⅳ．Some Illustrative Results 686

1．Effects of Condensation on Spectra 687

2．Benzene 690

3．Paraffins,Polyethylene,and Polymers 693

Ⅴ．References 694

12．Dielectric phenomena＆by Charles P．Smyth 697

Ⅰ．Introduction 698

Ⅱ．Dielectric Theory 699

1．Dielectric Constant and Refractive Index 699

2．Dielectric Constant,Polarization,and Refraction 700

3．Dielectric Relaxation and Loss 702

4．Loss Due to d-c Conductance 707

5．Interfacial Polarization 707

6．Mixtures 708

Ⅲ．Experimental Methods 709

1．Introduction 709

2．Dielectric Constant and Loss Measurement 709

Ⅳ．Dielectric Constants and Losses 713

1．Nonpolar Substances 713

2．Polar Substances 715

3．High Polymers 734

Ⅴ．Electrets 739

Ⅵ．References 740

13．Electron transfer across the boundaries of organic solids＆by Lawrence E．Lyons 745

Ⅰ．Introduction 746

1．Types of Organic Solids 746

2．Energy-Level Diagrams 747

3．Electrical Charge and Potential in Molecular Crystals 753

4．Electrets 757

Ⅱ．Solid-Vacuum Interfaces 759

1．Surface Potential，φS 759

2．Electron Affinities 764

3．Electron Emission from Organic Crystals Caused by Heat 767

4．Electron Emission Caused by Light 769

5．Secondary Electron Emission 784

6．Electron Emission by Stripping 784

7．Exo-Electrons 785

Ⅲ．Solid-Liquid Interfaces 785

1．Organic Solid in Contact with an Electrolyte 785

2．Metal in Contact with an Organic Solute or Liquid 788

Ⅳ．Solid-Solid Interfaces 788

1．Energy-Level Diagrams 788

2．Contact-Porential Differences,C 790

3．Contact Electrification 793

4．Point-Contact Rectification 796

5．Thermoelectric Effects 796

6．Photovoltaic Effects 799

Ⅴ．Conclusion 804

Ⅵ．References 804

Subject index 811