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Atomistic molecular dynamics simulations have been employed to study the self-ion (H + and OH - ) distribution at the interface between long-chain C 16 -OH alcohol (cetyl alcohol) monolayer and water. It is well known that the free air-water interface is acidic due to accumulation of the hydronium (H 3 O + ) ions at the interface. In the present study, we have observed that contrary to the air-water interface, at the long-chain alcohol monolayer-water interface, it is the hydroxide (OH - ) ion, not the hydronium ion (H 3 O + ) that gets accumulated. By calculating the potential of mean forces, it is confirmed that there is extra stabilization for the OH - ions at the interface relative to the bulk, but no such stabilization is observed for the H 3 O + ions. By analyzing the interaction of the self-ions with other constituents in the medium, it is clearly shown that the favorable interaction of the OH - ions with the alcoholic -OH groups stabilizes this ion at the interface. By calculating coordination numbers of the self-ions it is observed that around 50% water neighbors are substituted by alcoholic -OH in case of the hydroxide ion at the interface, whereas in the case of hydronium ions, only 15% water neighbors are substituted by the alcoholic -OH. The most interesting observation about the local structure and H-bonding pattern is that the hydroxide ion acts solely as the H-bond acceptor, but the hydronium ion acts only as the H-bond donor.

Residence time distribution (RTD) measurements were carried out in a packed bed column designed for exchange of hydrogen isotopes. The main objective of the study was to characterize the liquid phase mixing under various processes and operating conditions. The packed bed was composed of a mixture of two different types of catalytic packing materials, i.e., a hydrophobic material and a hydrophilic material. Technitium-99m ( 99m Tc) as sodium pertechnetate was used as a radiotracer for RTD measurements. From the measured RTD curves, mean residence times (MRTs), liquid holdup and degree of mixing of liquid phase were evaluated. An axial dispersion model exchange with stagnant zones was used to simulate the measured RTD curves. The results of model simulation showed that volume fraction of hydrophobic to hydrophilic packing and gas/liquid superficial velocities affect the liquid holdup, bed pressure drop and liquid phase dispersion/mixing characteristics. The results of the present study will help to screen packing, optimize the volume of the packing fractions, design and construct the catalyst and optimize the operating conditions for scale up of the isotope exchange process., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Holdup and axial dispersion of liquid phase in a catalytic exchange column were investigated by measuring residence time distributions (RTD) using a radiotracer technique. RTD experiments were independently carried out with two different types of packings i.e. hydrophobic water-repellent supported platinum catalyst and a mixture (50% (v/v)) of hydrophobic catalyst and a hydrophillic wettable packing were used in the column. Mean residence times and hold-ups of the liquid phase were estimated at different operating conditions. Axial dispersion model (ADM) and axial dispersion with exchange model (ADEM) were used to simulate the measured RTD data. Both the models were found equally suitable to describe the measured data. The degree of axial mixing was estimated in terms of Peclet number (Pe) and Bodenstein number (Bo). Based on the obtained parameters of the ADM, correlations for total liquid hold-up (H T ) and axial mixing in terms of Bo were proposed for design and scale up of the full-scale catalytic exchange column., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Like-charge ion-pair formation in an aqueous solution of guanidinium chloride (GdmCl) has two important facets. On one hand, it describes the role of the arginine (ARG) side chain in aggregation and dimer formation in proteins, and on the other hand, it lends support for the direct mechanism of protein denaturation by GdmCl. We employ all-atom molecular dynamics simulations to investigate the effect of GdmCl concentration on the like-charge ion-pair formation of guanidinium ions (Gdm(+)). From analyses of the radial distribution function (RDF) between the carbon atoms of two guanidinium moieties, the existence of both contact pairs and solvent-separated pairs has been observed. Although the peak height corresponding to the contact-pair state decreases, the number of Gdm(+) ions in the contact-pair state actually increases with increasing GdmCl concentration. We have also investigated the effect of the concentration of Gdm(+) on the structure of water. The effect of GdmCl concentration on the radial and tetrahedral structures of water is found to be negligibly small; however, GdmCl concentration has a considerable effect on the hydrogen-bonding structure of water. It is demonstrated that the presence of chloride ions, not Gdm(+), in the first solvation shell of water causes the distortion in the hydrogen-bonding network of water. In order to establish that Gdm(+) not only stacks against another Gdm(+) but also directly attacks the ARG residue of a protein or peptide, simulation of an ARG-rich peptide in 6 M aqueous solution of GdmCl has been performed. The analyses of RDFs and orientation distributions reveal that the Gdm(+) moiety of the GdmCl attacks the same moiety in the ARG side chain with a parallel stacking orientation.