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