PHYSICAL CHEMISTRY

By KENNETH SMITH

CONTENTS INTRODUCTION TO POLYMER PHYSICAL CHEMISTRY TARGETS OF THIS BOOK DEFINITION OF TERMS IRREGULARITY OF POLYMERS NONUNIFORMITY OF MONOMER CONNECTION IN A CHAIN POLYDISPERSITY IN AN ENSEMBLE OF CHAINS DERIVATION OF THE SCHULZ–FLORY DISTRIBUTION DERIVATION OF THE SCHULZ–ZIMM DISTRIBUTION CHARACTERISTIC AVERAGES OF THE SCHULZ–FLORY AND SCHULZ–ZIMM DISTRIBUTION PROPERTIES OF POLYMERS IN CONTRAST TO LOW MOLAR MASS MATERIALS POLYMERS AS SOFT MATTER HISTORY OF POLYMER SCIENCE IDEAL POLYMER CHAINS COIL CONFORMATION MICRO- AND MACROCONFORMATIONS OF A POLYMER CHAIN MEASURES OF SIZE OF A POLYMER COIL SIMPLE CHAIN MODELS THE RANDOM CHAIN (PHANTOM CHAIN, FREELY JOINTED CHAIN) THE FREELY ROTATING CHAIN THE CHAIN WITH HINDERED ROTATION THE KUHN MODEL THE ROTATIONAL ISOMERIC STATES MODEL ENERGETIC VERSUS ENTROPIC INFLUENCE ON THE SHAPE OF A POLYMER THE PERSISTENCE LENGTH SUMMARY THE GAUSSIAN COIL THE DISTRIBUTION OF END-TO-END DISTANCES RANDOM-WALK STATISTICS THE FREE ENERGY OF IDEAL CHAINS DEFORMATION OF IDEAL CHAINS ENTROPY ELASTICITY A SCALING ARGUMENT FOR THE DEFORMATION OF IDEAL CHAINS SELF-SIMILARITY AND FRACTAL NATURE OF POLYMERS REAL POLYMER CHAINS INTERACTION POTENTIALS AND EXCLUDED VOLUME CLASSIFICATION OF SOLVENTS OMNIPRESENCE OF THE ?-STATE IN POLYMER MELTS THE CONFORMATION OF REAL CHAINS COIL EXPANSION FLORY THEORY OF A POLYMER IN A GOOD SOLVENT DEFORMATION OF REAL CHAINS CHAIN DYNAMICS BROWNIAN MOTION AND DIFFUSION THE ROUSE MODEL THE ZIMM MODEL RELAXATION MODES SUBDIFFUSION VALIDITY OF THE MODELS POLYMER THERMODYNAMICS THE FLORY–HUGGINS MEAN-FIELD THEORY THE ENTROPY OF MIXING THE ENTHALPY OF MIXING THE FLORY–HUGGINS PARAMETER AS A FUNCTION MICROSCOPIC DEMIXING SOLUBILITY PARAMETERS PHASE DIAGRAMS EQUILIBRIUM AND STABILITY CONSTRUCTION OF THE PHASE DIAGRAM MECHANISMS OF PHASE TRANSITIONS SPINODAL DECOMPOSITION NUCLEATION AND GROWTH OSMOTIC PRESSURE CONNECTION OF THE SECOND VIRIAL COEFFICIENT, A2, TO THE FLORY–HUGGINS PARAMETER, ?, AND THE EXCLUDED VOLUME, VE MECHANICS AND RHEOLOGY OF POLYMER SYSTEMS FUNDAMENTALS OF RHEOLOGY ELEMENTARY CASES OF MECHANICAL RESPONSE DIFFERENT TYPES OF DEFORMATION IN RHEOLOGY THE TENSOR FORM OF HOOKE’S LAW VISCOELASTICITY ELEMENTARY TYPES OF RHEOLOGICAL EXPERIMENTS THE RELAXATION EXPERIMENT THE CREEP TEST THE DYNAMIC EXPERIMENT COMPLEX MODULI VISCOUS FLOW METHODOLOGY IN RHEOLOGY OSCILLATORY SHEAR RHEOLOGY MICRORHEOLOGY ACTIVE MICRORHEOLOGY PASSIVE MICRORHEOLOGY PRINCIPLES OF VISCOELASTICITY VISCOELASTIC FLUIDS: THE MAXWELL MODEL VISCOELASTIC SOLIDS: THE KELVIN–VOIGT MODEL MORE COMPLEX APPROACHES SUPERPOSITION PRINCIPLES THE BOLTZMANN SUPERPOSITION PRINCIPLE THE THERMAL ACTIVATION OF RELAXATION PROCESSES TIME–TEMPERATURE SUPERPOSITION VISCOELASTIC STATES OF A POLYMER SYSTEM QUALITATIVE DISCUSSION OF THE MECHANICAL SPECTRA QUANTITATIVE DISCUSSION OF THE MECHANICAL SPECTRA RUBBER ELASTICITY CHEMICAL THERMODYNAMICS OF RUBBER ELASTICITY STATISTICAL THERMODYNAMICS OF RUBBER ELASTICITY SWELLING OF RUBBER NETWORKS TERMINAL FLOW AND REPTATION THE TUBE CONCEPT ROUSE RELAXATION AND REPTATION REPTATION AND DIFFUSION CONSTRAINT RELEASE SCATTERING ANALYSIS OF POLYMER SYSTEMS BASICS OF SCATTERING SCATTERING REGIMES STRUCTURE AND FORM FACTOR LIGHT SCATTERING STATIC LIGHT SCATTERING DYNAMIC LIGHT SCATTERING CLOSING REMARKS