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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: <smarttagtype namespaceuri="urn:schemas-microsoft-com:office:smarttags" name="metricconverter"> Single ion transfer entropies, <i style="">∆S</i><sup>0</sup><sub>t</sub>(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 Ph<sub>4</sub>AsPh<sub>4</sub>B TATB reference electrolyte assumption, and solubility of the salts measured at 15°, 20°, 30° and 35°C, and that at 25 °C reported earlier. <i style="">∆S</i><sup>0</sup><sub>t</sub>(i) of the ions as well as their chemical effects, <i style="">∆S</i><sup>0</sup><sub>t</sub>,<sub> ch</sub>(i) (as obtained after correcting for the cavity effects, <i style="">∆S</i><sup>0</sup><sub>t</sub>,<sub> cav</sub>(i) and ignoring Born-type electrostatic effect <i style="">∆S</i><sup>0</sup><sub>t</sub>,<sub>Born</sub>(i), since the solvent mixtures are isodielectric), exhibit mirror-image behaviour of simple cation like K<sup>+</sup> and anion like Cl<sup>-</sup>, which can be explained in the light of Kundu <i>et al.</i>’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 <i>T</i><i style="">∆S</i><sup>0</sup><sub>t, ch</sub>(i) serves as a useful probe for the 3D-structuredness of aqueous cosolvents. </smarttagtype>
Description: 504-511
ISSN: 0376-4710
Appears in Collections:IJC-A Vol.48A(04) [April 2009]

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