Der Pharma Chemica
Journal for Medicinal Chemistry, Pharmaceutical Chemistry, Pharmaceutical Sciences and Computational Chemistry
ISSN: 0975-413X
Abstract
Comparative Solvation Behaviour of Li+ and Na+ ions in Acetonitrile and Nitromethane Binary Mixtures at 298.15 K
Author(s): Hardeep Anand, Narender SinghMolar conductance of lithium perchlorate (LiClO4), sodium perchlorate (NaClO4), sodium tetraphenylborate (NaBPh4), tetrabutylammonium perchlorate (Bu4NClO4) and tetrabutylammonium tetraphenylborate (Bu4NBPh4) have been measured in the range 0.005-0.2 mol kg-1 in binary mixtures of acetonitrile (AN) and nitromethane ( NM) containing 0, 10, 20, 40, 60, 80 and 100 mol% of NM in AN at 298.15 K. The experimental data of conductance has been analyzed using Shedlovsky method to evaluate limiting molar conductance (??o) of these electrolytes which were further split to obtain limiting ionic conductances (בּo) of various ions present in salts. The ionic radii (ri) of ions in solutions were calculated using a modified form of Stoke’s law and were analyzed in the aspects of ion-solvent interactions. The solvated radii (ri) of Li+ and Na+ ions were found to be greater than rest of the ions in the entire solvent composition range which indicates strong solvation of the ions. Bu4N+ and Ph4B- ions were found to show poor solvation due to solvophobic interaction. Solvated radii (ri) values indicate preferential solvation of Li+ and Na+ ions in the intermediate solvent composition range than in pure AN and NM. Li+, however, is found to be better solvated than Na+ in AN+ NM binary mixtures at all compositions.
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