Ionic Recation Design. Solvent and Salt Effects

Clements, Luther D.; Eckert, Charles A.

doi:10.1021/i260039a021

Cited by 2 publications

(1 citation statement)

References 15 publications

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“…In most reactions involving ions in solution, the overwhelmingly dominant factor is the relative solvation of ionic reactants, transition state, and products, and virtually all other effects are second-order. For example, by including solvation by the method of Scatchard (1923bScatchard ( , 1936, Clements and Eckert (1971) were able to extend predictions of the salt effect on the rate of an ion-ion reaction in several solvents up to ionic strengths of about unity, as shown for the bromoacetate-thiosulfate reaction in water in Figure 9.…”

Section: Ionic Solutionrmentioning

confidence: 99%

Molecular thermodynamics for chemical reaction design

1974

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Various techniques of molecular thermodynamics and solution theory have been applied, through the transition state theory, to problems in chemical kinetics. These include experimental techniques for ascertaining the structure and properties of the transition states for various classes of reactions, plus analytical methods for using this information to predict the effect of solvents or reactant structure on chemical reaction rates. Such methods provide the chemical engineer with an additional parameter to use in the optimal design of reaction systems–that is, the chemistry of the reaction itself.

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Section: Ionic Solutionrmentioning

confidence: 99%

Molecular thermodynamics for chemical reaction design

1974

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Activation Parameters of Bromoacetate–Thiosulfate Reaction in Ethylene Glycol–Water Mixtures

Biswas¹,

Maula²,

Das³

1987

Bulletin of the Chemical Society of Japan

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The activation parameters for the reaction between bromoacetate (\barR) and S2O32− ions in water and aqueous mixtures of ethylene glycol (5–50% by weight) have been evaluated from the rate constants, corresponding to zero ionic strength, at 15, 25, and 35 °C. The standard free energies of transfer (ΔGtr°) of the reacting ions and hence of the transition state (ΔGtr#) from water to the mixed media at 25 °C have been determined from the measured solubilities of AgR, TlCl, and Tl2S2O3 in the different media, using the reported values of ΔGtr° of Ag+ and Cl− ions. Attempts have been made to interpret the kinetic results in the light of solvent properties and free energies of transfer. Although both the reacting ions are destabilized, on adding glycol to the medium, the larger destabilization of the transition state, arising from decreased dielectric constant as well as solvating capacity of the medium, outweighs the combined effects on the reactants leading to reduced reaction rates.

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Ionic Recation Design. Solvent and Salt Effects

Abstract: The Br^nsted-Bjerrum equation is applied to predict variations in rates of ionic chemical reactions as a function of the reaction medium. Experimental rate constants are reported for the reaction of bromoacetate and thiosulfate ions over a range of concentration,

Cited by 2 publications

References 15 publications

Molecular thermodynamics for chemical reaction design

Molecular thermodynamics for chemical reaction design

Activation Parameters of Bromoacetate–Thiosulfate Reaction in Ethylene Glycol–Water Mixtures

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