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Title: Single-ion transfer energetics of some ions based on TATB assumption in aqueous mixtures of N,N-dimethylformamide
Authors: Ray, S K
Sarkar, S
Sinha, S
Kundu, K K
Issue Date: Sep-1994
Publisher: NISCAIR-CSIR, India
Abstract: Single-ion transfer energies G(i) and entropies S(i) of some electrolytes from water to 20, 40, 60 and 80 wt % aqueous N,N-dimethylformamide (DMF) solvents have been determined at 25°C using the widely used tetraphenylarsonium tetraphenylborate (Ph4AsPh4B, TATB) reference electrolyte (RE) assumption from solubility and emf measurements at five temperatures in the range 15-35°C.Analysis of G(i) values of the ions as well as the chemical effects, G, ch(i), as obtained after correcting for the cavity effects, G, cav(i), estimated by the scaled particle theory (SPT) and the Born as well as ion-dipole type electrostatic effects, estimated by use of simple Born and Kim formulations respectively, reveals that cationophilicity, aninophobicity and/or predominant dispersion interactions of the solvent mixtures are guiding the solvation behaviour of the ions. But the corresponding TS(i) values obtained after due correction of the cavity and Born-type electrostatic effects from TS,ch(i) values, reveal the mirror image entropic behaviour of simple cations and anions that can be explained in the light of Kundu etal.'s four-step transfer process.
Page(s): 805-815
ISSN: 0975-0975(Online); 0376-4710(Print)
Appears in Collections:IJC-A Vol.33A(09) [September 1994]

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