Ion Exchange

Cover
Preface
Contents
Introduction
1. Elementary Principles
2. Structure and Properties of Ion Exchangers
2-1. Mineral Ion Exchangers
2-2. Synthetic Inorganic Ion Exchangers
2-3. Ion-Exchange Resins
2-5. Other Materials with Ion-Exchange Properties
2-6. Liquid Ion Exchangers
2-7. Survey and Comparison
Summary
References
3. Preparation
3-1. Principles
3-2. Cation Exchangers
Condensation Polymers
Addition Polymers
Specific Cation Exchangers
3-3. Anion Exchangers
Condensation Polymers
Addition Polymers
3-4. Amphoteric Ion Exchangers
3-5. Particle Shape and Size, Macroreticular Resins, and Supported Ion Exchangers
3-6. Ion-Exchanger Membranes
Collodion and Mineral Membranes
“Homogeneous” Membranes
“Heterogeneous” Membranes
“lnterpolymer” Membranes
Graft-copolymer Membranes
Impregnated Membranes
Summary
References
4. Capacity
4-1. Definitions and Units
4-2. Apparent Capacity and its Dependence on Experimental Conditions
4-3. pH TITRATION
4-4. Determination of pK Values
4-5. Experimental Methods
Summary
References
5. Equilibria
5-1. Theoretical Approaches and Models
5-2. Swelling
Principles and General Rules
Water of Hydration and "Free" Water
Water-vapor Sorption Isotherms
Quantitative Treatment
Swelling pressure and solvent activity
Determination of swelling pressures
Elasticity of the matrix
Osmotic coefficients
Thermodynamic functions
Other Approaches and Models
Solvation effects.
Incomplete dissociation of the fixed ionogenic groups
Electrostatic effects
Molecular models
Ion Exchangers with Particular Structure
Resins with inhomogeneous structure
Amphoteric ion exchangers
Crystalline ion exchangers
5-3. Sorption of Solutes
Sorption Isotherms and Distribution Coefficients
Sorption of Nonelectrolytes
Sorption of Strong Electrolytes
The Donnan potential
General rules
Quantitative treatment
Activity coefficients of sorbed electrolytes
Other theoretical approaches and models
Simultaneous Sorption of Electrolytes and Nonelectrolytes
Sorption of Weak Electrolytes
“Site Sharing"
5-4. Ion-Exchange Equilibria
Ion-exchange Isotherm, Separation Factor, Selectivity Coefficient,and Equilibrium Constant
Ion-exchange Isotherm
Separation Factor
Selectivity Coefficient
Distribution Coefficient
Thermodynamic Equilibrium Constant
Selectivity and Its Causes
Effect of counter-ion valences; ''electroselectivity.''
Ionic solvation and swelling pressure
Sieve action
Specific interactions in the ion exchanger
Association and complex formation in the solution
Formation of precipitates
Temperature and pressure
Quantitative Treatment
Ionic solvation and swelling pressure
Ion-pair formation and association
Prediction of Ion-exchange Equilibria
Calculation of Activity Coefficients in Solutions
Ion Exchangers of Particular Structure and Composition
Polyfunctional ion exchangers
Ion exchangers with inhomogeneous structure
Zeolites
Crystalline ion exchangers with layer structure
Other Theoreticaland Models
5-5. Systems with More Than Two Counter-Ion Species
5-6. Ion-Exchange Equilibria Involving Complexing Agents
Complex-ion Equilibria in Solutions
Equilibria with Cation Exchangers in the Presence of a Complexing Anion
Ion-exchange equilibria with one complex-forming cation
Trace-component systems
Macrocomponent systems with two complex-forming cations
Weak acids and buffer solutions as complexing agents
Polynuclear complexes and weak complex acids
Prediction of equilibria
Calculation of complex-stability constants
Equilibria with Anion Exchangers in the Presence of aComplexing Anion
Equilibria with one complex-forming cation
Prediction of equilibria, experimental evidence, and interpretation ofexperimental results
Calculation of complex-stability constants
Nonequilibrium in the Solution
5-7. “Ligand Exchange”
Sorption of ligands
Exchange of ligands
Interference by ion exchange
5-8. Reactions of Materials of Low Solubility
Dissolution by a cation or anion exchanger
Dissolution by mixtures of cation and anion exchangers
5-9. Experimental Methods
Conditioning and Storage
Equilibration and Separation from the Solution
Determination of Water or Solvent Content
Water-vapor Sorption Isotherms
Volume and Density Determinations
Sorption of Solutes
Ion-exchange Equilibria
Ion-exchange and Sorption Isotherms
Calorimetric Measurement
Summary
References
6. Kinetics
6-1. Mechanism of Ion Exchange
6-2. The Rate-Determining Step
6-3. Rate Laws of Ion Exchange
Fundamentals
Isotopic exchange
Particle diffusion control
Film diffusion control
Intermediate range between particle and film diffusion control
Time requirement for exhaustion of the solution
Experimental evidence
Ion Exchange
Ideal limiting laws
Derivation of the criterion for the rate-determining step
Deviations in actual systems
Experimental evidence
Exchange of Trace Components
Prediction of Ion-exchange Rates
General Rules
6-4. Emperical and Simplified Rate Laws
6-5. Systems with More Than Two Counter-Ion Species
6-6. Kinetics of Sorption and Swelling
Sorption and Desorption of Salutes
Sorption and desorption of nonelectrolytes
Sorption and desorption of electrolytes
Swelling and Shrinking
Experimental Evidence
6-7. Reactions of Materials of Low Solubility
6-8. Diffusion Coefficients in Ion Exchangers
Theoretical Considerations
Experimental Evidence
Size of the Species
Valence and Chemical Nature of the Species
Swelling and Mesh Width of the Ion Exchanger
Concentration of Fixed Ionic Groups and Chemical Nature of tire Matrix
Composition of the Pore Liquid
Temperature
6-9. Experimental Methods
Ion-exchange Materials
Rate of Ion Exchange
Batch Technique
Shallow-bed Technique
Determination of Diffusion Coefficients in Ion Exchangers
Isotopic exchange between ion exchangers and solutions
Isotopic redistribution within insulated ion exchangers
Steady-state isotopic diffusion across membranes
Other methods
Summary
References
7. Electrochemical Properties
7-1. Electric Conductivity
7-2. Transference Numbers and Transport Numbers
7-3. Transference of solvent; Convection conductivity
7-4. Quantitative Relations
7-5. Experimental Methods
Summary
References
8. Ion-Exchanger Membranes
8-1. Characteristic Properties of Ion-Exchanger Membranes
8-2. Models and Theoretical Approaches
8-3. Diffusion Across Membranes
Self-diffusion and Isotopic Diffusion
Diffusion of an Electrolyte
Interdiffusion of Counter Ions
Bi-ionic systems
Diffusion of a Nonelectrolyte
8-4. Membrane Potentials
Membrane Potential, Electrode Potentials, and EMF
Phase-boundary Potentials (Donnan Potentials)
Concentration Potentials
Bi-ionic Potentials
Complete Membrane Diffusion Control
Complete Film Diffusion Control
Partial Film Diffusion Control
Extension to Other Bottndary Conditions
Experimental Evidence
Multi-ionic Potentials
Nonisothermal Membrane Potentials
8-5. General Integration of the Nernst-Plank Equations
8-6. Anomalous Osmosis
8-7. Streaming Potential, Streaming Current, And Electrolyte Filtration
Streaming potential
Streaming current
Electrolyte filtration
8-8. Transport of Electric Current Across Membranes
Ionic Transference and Electrodialysis
Electroosmosis
Cells with Solutions of Different Concentrations
8-9. Sorting Effects
8-10. Experimental Methods
Measurement of Ionic Fluxes and Concentration Profiles
Measurement of Membrane Potentials
Measurement of Transference Numbers, Electroosmosis,and Permeabilities
Summary
References
9. Ion-Exchange Columns
9-1. Ion Exchange in Columns
9-2. Conventional Column Operation
9-3. Two-Stage, Multistage, and Mixed-Bed Deionization
9-4. Ion Exclusion
9-5. Ion Retardation
9-6. Separation by Selective Displacement
9-7. Principles of Ion-Exchange Chromatograpgy
Displacement Development
Elution Development
Frontal Analysis
Use of Complexing Agents
Partition Chromatography with Ion Exchangers
9-8. “Ligand Exchange” and Other Techniques Based on Chemical Reactions
9-9. Quantitative Treatment
Theoretical Approaches, Models, and Assumptions
Rate Theories
Elution development of trace quantities
Displacement processes
Equilibrium Theories
General Comments
9-10. Hydrodynamic and Thermochemical Effects
Hydrodynamic Aspects
Eddy dispersion
Flow moldistribution
“Fingering”
Thermochemical Effects
9-11. Electrochemical Properties
Models
Electric Conductivity
Concentration Potentials
Application of the Model to Leaky Membranes
9-12. Experimental Methods
Simple Laboratory Columns
Determination of Effluent Concentration Histories
Electrochemical Measurements
Summary
References
10. Behavior in Nonaqueous and Mixed Solvents
10-1. Ion Exchange in Nonaqueous Systems
10-2. Swelling
Swelling in Pure Solvents
Selective Swelling in Mixed Solvents
10-3. Capacity
10-4. Ion-Exchange and Sorption Equilibria
I0-5. Kinetics
10-6. Electrochemical Properties
Summary
References
11. Catalysis by Ion Exchangers
11-1. Reactions of Gases and Vapors
11-2. Reactions of Liquids and Solutes
Mechanism
Catalyst Selectivity
11-3. Kinetics
The Rate-determining Step
Reaction Rate and Catalyst Performance
Internal reaction control
Effect of intraparticle diffusion
Experimental evidence
Order and Activation Energy of the Overall Process
Comparison with Homogeneous Catalysis; Catalyst Efficiency
Prediction of the Rate-determining Step and the Reaction Rate
Selection of Catalysts and Operating Conditions
11-4. Experimental Methods
Summary
References
12. Electron Exchangers and Redox Ion Exchangers
12-1. Preparation
Condensation polymers
Addition polymers
Introduction of reactive groups after polymerization
Redox ion exchangers
12-2. Reactions and Applications
12-3. Physicochemical Properties
Redox Capacity
Redox Potential
Redox potentials of redox couples in solution
Redox potentials of electron exchangers
Kinetics
12-4. Experimental Methods
Determination of Redox Capacity
Standard Redox Potential and Potentiometric Titration
Summary
References
Appendix
Symbols, Abbreviations, and Units
Physical Quantities
Subscripts, Superscripts, etc.
Physical Constants
Units and Conversion Factors
Mathematical Symbols
Commercial Ion Exchangers
Tables of Mathematical Functions
Name Index
Subject Index