Ion Exchange in Analytical Chemistry

Preface

Chapter 1 Introduction

A. History of Ion Exchange

B. Synthesis of Ion-Exchange Resins

I. Synthesis of Cation-Exchange Resins

II. Synthesis of Anion-Exchange Resins

III. Polyfunctionality of Polystyrene Resins

C. List of Ion-Exchange Resins

References

Chapter 2 General Properties of Ion-exchange Resins

A. Stability

I. Thermal Stability

II. Resistance to Reagents

III. Resistance to Radiation

IV. Mechanical Stability

B. Equivalence of Exchange Reactions

C. Reversibility of Ion-Exchange Reactions

D. Conversion of the Resin from One Form to Another

E. Titration Curves and Capacity

I. Procedure for the Titration of a Resin

II. Procedure for the Determination of Capacity

F. Crosslinking and Swelling

I. Measurement of Swelling

II. Flotation Test for Uniformity of Crosslinking

G. Donnan Equilibrium

I. Sulphonated Polystyrene Resins

II. Measurement of Donnan Invasion

III. Strong-Base Anion-Exchange Resins

H. Absorption of Nonelectrolytes

I. Absorption or Adsorption

I. Catalysis by Ion-Exchange Resins

References

Chapter 3 Ion-Exchange Equilibrium

A. The Equilibrium Distribution

I. The Selectivity Coefficient

II. Partition Ratios

III. Electroselectivity

B. Thermodynamics of Ion Exchange

I. The Equilibrium Constant

II. Enthalpy and Entropy

C. Ionic Selectivity

I. Experimental Data

II. Theoretical Treatment

III. Resins as Nonaqueous Solvents

D. Experimental Methods

I. Shaking

II. Tracer-Pulse and Concentration-Pulse Methods

References

Chapter 4 Ion-exchange Kinetics

A. The Rate-Controlling Step

B. Experimental Methods

I. Shallow-Bed Method

II. Limited-Bath Method

III. Indicator Method

C. Conditions that Influence the Rate

I. Particle Size

II. Diffusion Coefficient Inside the Resin

III. Diffusion Coefficient in the Aqueous Film

IV. Stirring

V. Concentration of the Solution

References

Chapter 5 Nonchromatographic Applications

A. Preparation, Care, and Use of an Ion-Exchange Column

I. The Tube

II. The Resin

B. Preparation and Purification of Reagents

I. Deionization

II. Miscellaneous Ion-Exchange Methods for the Preparation and Purification of Reagents

C. Removal of Interfering Constituents

I. Removal of Interfering Cations

II. Removal of Interfering Anions

III. Miscellaneous Analytical Separations

D. Determination of Total Salt

I. Sources of Error

II. Applications

E. Dissolving Insoluble Salts

I. Applications

F. Concentrating Trace Constituents

I. From Solutions Containing no Electrolyte in Large Concentration

II. From Solutions Containing Large Concentrations of Electrolytes

III. Microqualitative Spot Tests

References

Chapter 6 Theory of Ion-exchange Chromatography

A. Subdivisions of Ion-Exchange Chromatography

I. Ion-Exchange Elution Chromatography

II. Ion-Exchange Frontal Chromatography

III. Ion-Exchange Displacement Chromatography

IV. Relative Advantages of the Three Methods

B. Importance of Theoretical Considerations

C. Plate Theory of Ion-Exchange Elution Chromatography

I. History of the Plate Theory

II. Assumptions of the Plate Theory

III. Equation for the Peak Volume of an Elution Curve

IV. Effect of Concentration of Eluent

V. Effect of pH of Eluent

VI. Effect of Complexing Agents in the Eluent

VII. Equation of the Elution Curve

VIII. Calculation of U* if the Eluent is Changed during the Elution

IX. Width of Elution Curves

X. Procedure for Developing a Method of Separation by Ion-Exchange Elution Chromatography

D. Mass-Transfer or Continuous-Flow Plate Theory

I. The Model of Glueckauf

E. Tracer-Pulse and Concentration-Pulse Methods

I. Relation Between Elution Volume and Partition Ratio

II. The Tracer-Pulse Method

III. The Concentration-Pulse Method

References

Chapter 7 Technique of Ion-Exchange Chromatography

A. Preparation of the Column

I. Size of Resin

II. Evenness of Packing

III. Determination of Void Volume and Exchange Capacity

B. Performing the Elution

I. Applying the Sample to the Column

II. Maintenance of Flow Rate

C. Analyzing the Effluent

I. Fraction Collectors

II. Chemical Analysis

References

Chapter 8 Applications of Ion-Exchange Chromatography

A. Separation of Inorganic Ions

I. Metals

II. Nonmetals

B. Separation of Organic Compounds

I. Cations

II. Anions

III. Uncharged Molecules

References

Chapter 9 Salting-Out Chromatography and Related Methods

A. Ion Exclusion

B. Separations by Elution with Water or Dilute Aqueous Buffer Solutions

C. Salting-Out Elution Chromatography

I. Theory of Salting-Out Elution Chromatography

II. Applications of Salting-Out Elution Chromatography

D. Elution Chromatography with Mixed Solvents

I. Elution Solubilization Chromatography

II. Elutions of Very Hydrophilic Nonelectrolytes with Mixed Solvents

III. Elutions with Dilute Buffers in Nonaqueous or Mixed Solvents

IV. Salting-Out Elution Chromatography with Mixed Solvents

E. Comparison with Gas-Liquid Chromatography

I. Advantages of Gas-Liquid Chromatography

II. Advantages of Chromatography Through Ion-Exchange Resins

F. Frontal Liquid-Resin Chromatography

References

Chapter 10 Less Common Ion Exchangers

A. Porous Resins

I. Dowex 21K

II. Macroreticular Resins

III. Applications of Porous Resins

B. Resins with Interpenetrating Polymer Networks

C. Ion-Retardation Resins

D. Ion-Exchange Membranes

I. Preparation of Ion-Exchange Membranes

II. Properties of Ion-Exchange Membranes

III. Applications of Ion-Exchange Membranes

E. Inorganic Ion Exchangers

I. Hydrous Oxides

II. Salts of Multivalent Metals

III. Salts of Heteropoly Acids

IV. Molecular Sieves

V. Other Inorganic Exchangers

F. Liquid Ion Exchangers

I. Liquid Anion Exchangers

II. LiquiDd Cation Exchangers

III. Desirable Properties

IV. Comparison with Ion-Exchange Resins

V. Theory

VI. Applications of Liquid Ion Exchangers

G. Ion-Exchange Paper

I. Theory of Chromatography with Ion-Exchange Paper

II. Ion-Exchange Cellulose

III. Ion-Exchange-Resin Paper

IV. Paper Impregnated with Inorganic Exchangers

V. Paper Impregnated with Liquid Ion Exchangers

VI. Comparison of Paper Chromatography with Column Chromatography

H. Ion-Exchange Materials from Carbohydrates

I. Preparation of Cellulosic Ion Exchangers

II. Applications of Cellulosic Ion Exchangers

I. Thin-Layer Chromatography

I. Cellulosic Exchangers

II. Ion-Exchange Resins

III. Other Exchangers

J. Chromatographic Resolution of Racemic Substances

I. Optically Active Anion-Exchange Materials

II. Optically Inactive Resins with Optically Active Counterions

III. Chromatographic Separation of Diastereoisomers with an Optically Inactive Stationary Phase

References

Chapter 11 Study of Complex Ions

A. Separation of Kinetically Stable Complexes

B. Measurement of Stability Constants by Ion Exchange

I. Equilibrium Studies with Cation-Exchange Resins

II. Stability Constants by Paper Chromatography

III. Resin Membranes

IV. Anion-Exchange Resins

C. Anionic Chloride Complexes

D. Metal-Ammonia and Metal-Amine Complexes

References

Appendix. List of Symbols

Table A.1

Name Index

Subject Index

Other Titles in the Series