• Hemant K Kashyap

      Articles written in Journal of Chemical Sciences

    • Non-ideality in Born-free energy of solvation in alcohol-water and dimethylsulfoxide-acetonitrile mixtures: Solvent size ratio and ion size dependence

      Hemant K Kashyap Ranjit Biswas

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      Recent extension of mean spherical approximation (MSA) for electrolyte solution has been employed to investigate the non-ideality in Born-free energy of solvation of a rigid, mono-positive ion in binary dipolar mixtures of associating (ethanol-water) and non-associating (dimethylsulfoxide-acetonitrile) solvents. In addition to the dipole moments, the solvent size ratio and ion size have been treated in a consistent manner in this extended MSA theory for the first time. The solvent-solvent size ratio is found to play an important role in determining the non-ideality in these binary mixtures. Smaller ions such as Li+ and Na+ show stronger non-ideality in such mixtures compared to bigger ions (for example, Cs+ and Bu4N+). The partial solvent polarization densities around smaller ions in tertiary butanol (TBA)-water mixture is found to be very different from that in other alcohol-water mixtures as well as to that for larger ions in aqueous solutions of TBA. Non-ideality is weaker in mixtures consisting of solvent species possessing nearly equal diameters and dipole moments and is reflected in the mole fraction dependent partial solvent polarization densities.

    • Solvent sorting in (mixed solvent + electrolyte) systems: Time-resolved fluorescence measurements and theory

      Harun Al Rasidgazi Hemant K Kashyap Ranjit Biswas

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      In this manuscriptwe explore electrolyte-induced modification of preferential solvation of a dipolar solute dissolved in a binary mixture of polar solvents. Composition dependence of solvation characteristics at a fixed electrolyte concentration has been followed. Binary mixtures of two different polarities have been employed to understand the competition between solute-ion and solute-solvent interactions. Time-resolved fluorescence Stokes shift and anisotropy have been measured for coumarin 153 (C153) in moderately polar (ethyl acetate + 1-propanol) and strongly polar (acetonitrile + propylene carbonate) binary mixtures at various mixture compositions, and in the corresponding 1.0M solutions of LiClO4. Both the mixtures show red shifts in C153 absorption and fluorescence emission upon increase of mole fraction of the less polar solvent component in presence of the electrolyte. In addition, measured average solvation times become slower and rotation times faster for the above change in the mixture composition. A semi-molecular theory based on solution density fluctuations has been developed and found to successfully capture the essential features of the measured Stokes shift dynamics of these complex multi-component mixtures. Dynamic anisotropy results have been analyzed by using both Stokes-Einstein-Debye (SED) and Dote-Kivelson-Schwartz (DKS) theories. The importance of local solvent structure around the dissolved solute has been stressed.

    • Three-dimensional Morphology and X-ray Scattering Structure of Aqueous tert-Butanol Mixtures: A Molecular Dynamics Study

      SUPREET KAUR HEMANT K KASHYAP

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      It is well established that water-alcohol mixtures exhibit anomalous properties at very low as well as at very high alcohol concentrations. Almost all the studies in this regard intend to link these anomalies to the microscopic structural changes as water (or alcohol) concentration increases in the mixture. However, it isimportant to note that the nature of these structural changes could be different at the water- and TBA-rich concentrations. In this article, our goal is to address such structural change overs, if really present, in the mixtures of water and tert-butanol (TBA) by using simulated X-ray scattering structure function, S(q), real space radial and spatial distribution functions and heterogeneity order parameter. By using a judicial partitioning scheme, we show that structural characteristic of pure water is qualitatively retained for XTBA < 0.1. The simulated S(q) peaks at around q=2 and q=2.8 Å⁻¹, which correspond to water oxygen correlations, begin to fade away only after XTBA ≥ 0.1. This is a clear indication of microscopic structural transition at XTBA ≈ 0.1. Beyond XTBA = 0.1, the TBA structural features begin to take over to that of water. The peak at q=1.3 Å⁻¹ which primarily corresponds to nonpolar-nonpolar correlations in pure TBA begin to rise at XTBA ≈ 0.1. However, the pre-peak at around q=0.75 Å⁻¹, which is due to polar-polar and nonpolar-polar correlations in pure TBA, seems to appear at lower q value only at the equi-molar concentration of the mixture. From the solvent cage surrounding the TBA molecules, we observe that while the aggregation of TBA alkyl groups, due to hydrophobic interaction, is maximum at 10% TBA, the intervening hydrogen bonding interactions between water and TBA molecules tend to lower the hydrophobic interactions between the alkyl groups of alcohol with increasing concentration of TBA. In addition to this, we also observe dimers and small clusters of water molecules in the TBA-rich regime. The computed heterogeneity order parameters for the individual components of the mixture reveal enhanced non-uniform distribution of the TBA molecules near XTBA ≈ 0.1 to 0.3. These results are also supported by the radial distribution functions and nearest neighbour coordination numbers of water and TBA oxygen atoms around TBA oxygen.

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