Abstract
Ion-exchange reactions between aqueous electrolyte solutions and organic ion exchangers are temperature dependent, and therefore they must be accompanied by the evolution or the absorption of heat. However, the magnitudes of these thermal effects generally are small so that they are measured best with a calorimeter rather than estimated by application of the van’t Hoff equation to the variation of the thermodynamic equilibrium constant with temperature. Calorimetrically determined ion-exchange reaction enthalpy changes are useful further in that they may be combined with free energies computed from equilibrium measurements to obtain the change in entropy. The sign and magnitude of the enthalpy and entropy changes afford an insight into the factors which govern the selective uptake of one ion in aqueous solution over another. For example, the entropy change frequently suggests that ion-solvent interactions are of central importance, while the enthalpy change may indicate that “site binding” or ion-pair formation by the ion exchanger governs the observed selective ion absorption.
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Selected Bibliography — Organic Ion Exchangers
G. E. Boyd, F. Vaslow, and S. Lindenbaum, “Heats of Exchange of the Alkali Metal Cations in Cross-linked Polystyrenesulfonates,” J. Phys. Chem., 68, 590 (1964).
S. Lindenbaum and G. E. Boyd, “Thermodynamic Quantities in the Exchange of Li+ with Cs+ Ion on Cross-linked Polymethacrylate Ion Exchangers,” J. Phys. Chem., 69, 2374 (1965).
F. Vaslow and G. E. Boyd, “Thermodynamic Properties in the Exchange of Ag+ with Na+ Ions in Cross-linked Polystyrenesulfonate Cation Exchangers,” J. Phys. Chem., 70, 2295 (1966).
F. Vaslow and G. E. Boyd, “Heats of Exchange of Halide Ions in Cross-linked Strong-base Anion Exchangers,” J. Phys. Chem., 70, 2507 (1966).
K. E. Becker, S. Lindenbaum, and G. E. Boyd, “Thermodynamic Quantities in the Exchange of Li+ with Cs+ Ion on Cross-linked Phosphonic Acid Cation Exchangers,” J. Phys. Chem., 70, 3834 (1966).
E. Boyd, J. W. Chase, and F. Vaslow, “Structural Effects on the Enthalpy and Entropy of Dilution of Aqueous Solutions of Quaternary Ammonium Halides at 25°. Comparisons with Strong-base Anion Exchangers,” J. Phys. Chem., 71, 573 (1967).
G. E. Boyd and A. Schwarz, “Heat of Exchange of I- with Cl- Ions on a Unifunctional Weak-base Type Anion Exchanger at 25°,” J. Phys. Chem., 71, 1355 (1967).
G. E. Boyd, F. Vaslow, and S. Lindenbaum, “Thermodynamic Quantities in the Exchange of Zn++ with Na+ Ions in Cross-linked Polystyrenesulfonate Cation Exchangers at 25°,” J. Phys. Chem., 71, 2214 (1967).
G. E. Boyd, F. Vaslow, A. Schwarz, and J. W. Chase, “Thermodynamic Properties at 25° of Aqueous Solutions of p-Ethylbenzenesulfonic Acid and Its Alkali Metal Salts. Comparisons with Cross-linked Polystyrenesulfonate Cation Exchangers,” J. Phys. Chem., 71, 3879 (1967).
E. Boyd and O. V. Larson, “The Binding of Quaternary Ammonium Ions by Polystyrenesulfonic Acid Type Cation Exchangers,” J. Am. Chem. Soc., 89, 6038 (1967).
D. Bonner and J. R. Overton, “The Effect of Temperature on Ion Exchange Equilibria. IV. The Comparison of Enthalpy Changes Calculated from Equilibrium Measurements and Calorimetrically Measured Values,” J. Phys. Chem., 65, 1599 (1961).
H. Cruickshank and P. Meares, “Thermodynamics of Cation Exchange. I. Determination of the Heats and Free Energies of Exchange by Resins,” Trans. Faraday Soc, 53, 1289 (1957).
H. Cruickshank and P. Meares, “II. Comparison Between Resins and Concentrated Chloride Solutions”, Trans. Faraday Soc, 53, 1299 (1957).
H. Cruickshank and P. Meares, “III. Thermodynamic Properties of Resins Containing a Mixture of Cations,” Trans. Faraday Soc, 54, 174 (1958).
S. Flett and P. Meares, “IV. Uni-, bi-, and tervalent Ions on Dowex-50,” Trans. Faraday Soc, 62, 1469 (1966).
S. Flett and P. Meares, “V. The Excess Enthalpies of Some Mixed Resinates of Dowex-50,” J. Phys. Chem., 70, 1841 (1966).
R. Heumann and D. Patterson, “Heats of Potassium-Lithium Ion Exchange on Sulfonated Polystyrene Resins,” Canadian J. Chem., 44, 2139 (1966).
S. Redhina and J. A. Kitchener, “Thermodynamics of Ion Exchange Processes. System H, Na and Ag with Polystyrene Sulfonate Resins,” Trans. Faraday Soc., 59, 515 (1963).
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© 1968 Plenum Press
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Boyd, G.E. (1968). Thermal Effects in Ion-Exchange Reactions: Heats of Ion Exchange. In: Porter, R.S., Johnson, J.F. (eds) Analytical Calorimetry. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-0001-5_18
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DOI: https://doi.org/10.1007/978-1-4757-0001-5_18
Publisher Name: Springer, Boston, MA
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