T K Kundu
Articles written in Journal of Chemical Sciences
Volume 115 Issue 5-6 October 2003 pp 341-348
Composites of nanometre-sized copper core-copper oxide shell with diameters in the range 6.1 to 7.3 nm dispersed in a silica gel were synthesised by a technique comprising reduction followed by oxidation of a suitably chosen precursor gel. The hot pressed gel powders mixed with nanometre-sized copper particles dispersed in silica gel showed electrical resistivities several orders of magnitude lower than that of the precursor gel. Electrical resistivities of the different specimens were measured over the temperature range 30 to 300°C. Activation energies for the coreshell nanostructured composites were found to be a fraction of that of the precursor gel. Such dramatic changes are ascribed to the presence of an interfacial amorphous phase. The resistivity variation as a function of temperature was analysed on the basis of Mott’s small polaron hopping conduction model. The effective dielectric constant of the interfacial phase as extracted from the data analysis was found to be much higher than that of the precursor glass. This has been explained as arising from the generation of very high pressure at the interface due to the oxidation step to which the copper nanoparticles are subjected.
Volume 125 Issue 2 March 2013 pp 379-385
Density functional theory based studies have been performed to elucidate the role of methanol as an methane hydrate inhibitor. A methane hydrate pentagonal dodecahedron cage’s geometry optimization, natural bond orbital (NBO) analysis, Mullikan charge determination, electrostatic potential evaluation and vibrational frequency calculation with and without the presence of methanol using WB97XD/6-31++G(d,p) have been carried out. Calculated geometrical parameters and interaction energies indicate that methanol destabilizes pentagonal dodecahedron methane hydrate cage (1CH4@512) with and without the presence of sodium ion. NBO analysis and red shift of vibrational frequency reveal that hydrogen bond formation between methanol and water molecules of 1CH4@512 cage is favourable subsequently after breaking its original hydrogen bonded network.
Volume 125 Issue 5 September 2013 pp 1259-1266
Density functional theory (DFT)-based simulations have been performed to provide electronic structure property correlation based reasoning for conceptualizing the effect of encapsulated methane molecule on the formation of methane hydrate cages, the role of methanol and ethylene glycol as inhibitor and the role of tetra-hydro-furan (THF) and cyclopentane as promoter of methane hydrate. Geometry optimization of 512 cage, 51262 cage and 51264 cage with and without encapsulated methane and the cluster of 512 cage with ethylene glycol, methanol, cyclopentane have been performed by density functional theory using 𝜔B97X-D/6-31++G(d,p) method. Methane hydrate formation inhibition by methanol and ethylene glycol as well as methane hydrate stabilization by cyclopentane and tetrahydrofuran are critically analysed based on the interaction energy, free energy change, dipole moment and infrared frequency calculation. Calculation of free energy change for formation of methane hydrate with/without reagents at various temperature and pressure using optimized structure is reported here. It is observed that hydrogen bond between water molecules of clathrate 512 cages become stronger in the presence of cyclopentane and tetrahydrofuran but weaker/broken in the presence of ethylene glycol and methanol. Simulated results correspond well with experimental findings and can be useful for designing new inhibitor and promoter molecules for gas hydrate formation.