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IJC-A Vol.48A(04) [April 2009] >

Title: Single ion transfer entropies in binary mixtures of isodielectric protic ethylene glycol and dipolar aprotic N, N-dimethylformamide vis-à-vis 3D-structuredness of aqueous co-solvents
Authors: Dolui, B K
Bhattacharya, S K
Kundu, K K
Keywords: Thermodynamics
Single ion transfer entropies
Transfer entropies
Isodielectric solvents
Issue Date: Apr-2009
Publisher: CSIR
Abstract:  Single ion transfer entropies, ∆S0t(i) of some electrolytes like tetraphenylarsonium picrate, potassium tetraphenylborate, potassium picrate and potassium chloride from protic ethylene glycol to its isodielectric mixtures with 20, 40 and 60 wt % protophilic dipolar aprotic N,N-dimethylformamide have been determined at 25 °C using the Ph4AsPh4B TATB reference electrolyte assumption, and solubility of the salts measured at 15°, 20°, 30° and 35°C, and that at 25 °C reported earlier. ∆S0t(i) of the ions as well as their chemical effects, ∆S0t, ch(i) (as obtained after correcting for the cavity effects, ∆S0t, cav(i) and ignoring Born-type electrostatic effect ∆S0t,Born(i), since the solvent mixtures are isodielectric), exhibit mirror-image behaviour of simple cation like K+ and anion like Cl-, which can be explained in the light of Kundu et al.’s four step transfer process. However, this feature in completely non-aqueous solvent system is strikingly different from that in aquo-cosolvent systems studied earlier, and offers an indirect evidence that the ‘characteristic mirror-image relationship’ of simple cations and anions, in aqueous cosolvent systems, is, as contended earlier, associated with 3D-‘structuredness’ of aqueous cosolvent systems. This reiterates that T∆S0t, ch(i) serves as a useful probe for the 3D-structuredness of aqueous cosolvents.
Page(s): 504-511
ISSN: 0376-4710
Source:IJC-A Vol.48A(04) [April 2009]

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