Ce0.78Sn0.2Pt0.02O2-delta: A new non-deactivating catalyst for hydrogen production via water-gas shift reaction

We demonstrate the activity of Ce0.78Sn0.2Pt0.02O2-delta, a new catalyst, towards water-gas shift (WGS) reaction. Over 99.5% CO conversion to H-2 is observed at 300 +/- 25 degrees C. Based on different characterization techniques we found that the present catalyst is resistant to deactivation due to carbonate formation and sintering of Pt on the surface when subjected to longer duration of reaction conditions. The catalyst does not require any pre-treatment or activation between start-up/shut-down reaction operations. Formation of side products such as methane, methanol, formaldehyde, coke etc. was not observed under the WGS reaction conditions indicating the high selectivity of the catalyst for H-2. Temperature programmed reduction of the catalyst in hydrogen (H-2-TPR) shows reversible reduction of Ce4+ to Ce3+, Sn4+ to Sn2+ and Pt4+ to Pt-0 oxidation state with oxygen storage capacity (OSC) of 3500 mu mol g(-1) at 80 degrees C. Such high value of OSC indicates the presence of highly activated lattice oxygen. CO oxidation in presence of stoichiometric O-2 shows 100% conversion to CO2 at room temperature. The catalyst also exhibits 100% selectivity for CO2 at room temperature towards preferential oxidation (PROX) of residual CO in presence of excess hydrogen in the feed. (C) 2010 Elsevier B.V. All rights reserved.

A study of the spectrum of an acoustic field in shallow water due to noise sources at the surface

An expression for the spectrum and cross spectrum of an acoustic field measured at two vertically separated sensors in shallow water has been obtained for any correlated noise sources distributed over the surface. Numerical results are presented for the case where the noise sources, white noise and wind-induced colored noise, are contained within a circular disk centered over the sensors. The acoustic field is generally inhomogeneous except when the channel is deep. The coherence function becomes real for a large disk, for a radius greater than 25 times the depth of the channel, decreases with further increase of the size of the disk, and finally tapers off after certain limiting size, approximately given by 1/alpha, where alpha is the attenuation coefficient.

Support-Dependent Activity of Noble Metal Substituted Oxide Catalysts for the Water Gas Shift Reaction

The water gas shift reaction was carried out over noble metal ion substituted nanocrystalline oxide catalysts with different supports. Spectroscopic studies of the catalysts before and after the reaction showed different surface phenomena occurring over the catalysts. Reaction mechanisms were proposed based upon the surface processes and intermediates formed. The dual site mechanism utilizing the oxide ion vacancies for water dissociation and metal ions for CO adsorption was proposed to describe the kinetics of the reaction over the reducible oxides like CeO2. A mechanism based on the interaction of adsorbed CO and the hydroxyl group was proposed for the reaction over ZrO2. A hybrid mechanism based on oxide ion vacancies and surface hydroxyl groups was proposed for the reaction over TiO2. The deactivation of the catalysts was also found to be support dependent. Kinetic models for both activation and deactivation were proposed. (C) 2010 American Institute of Chemical Engineers AIChE J, 56: 2662-2676, 2010

Chemistry in Confined Spaces: High-Energy Conformer of a Piperidine Derivative is Favored Within a Water-Soluble Capsuleplex

Propyloxy-substituted piperidine in solution adopts a conformation in which its alkoxy group is equatorially positioned Surprisingly, two conformers of it that do not interconvert in the NMR time scale at room temperature have been found within an octa-acid capsule The serendipitous finding of the axial conformer of propyloxy-substituted piperidine within a supramolecular capsule highlights the value of confined spaces in physical organic chemistry.

Enhanced Pair Hydrophobicity in the Water-Dimethylsulfoxide (DMSO) Binary Mixture at Low DMSO Concentrations

We observe a surprisingly sharp increase in the pair hydrophobicity in the water climethylsulfoxide (DMSO) binary mixture at small DMSO concentrations, with the mole fraction of DMSO (x(D)) in the range 0.12-0.16. The increase in pair hydrophobicity is measured by an increase in the depth of the first minimum in the potential of mean force (PMF) between two methane molecules. However, this enhanced hydrophobicity again weakens at higher DMSO concentrations. We find markedly unusual behavior of the pure binary mixture (in the same composition range) in the diffusion coefficient of DMSO and in the local composition fluctuation of water, We find that, in the said composition range, the average coordination number of the methyl groups (of distinct DMSO) varies between 2.4 and 2.6, indicating the onset of the formation of a chain-like extended connectivity in an otherwise stable tetrahedral network comprising of water and DMSO molecules. We propose that the enhanced pair hydrophobicity of the binary mixture at low DMSO concentrations is due to the participation of the two methane molecules in the local structural order and the emerging molecular associations in the water-DMSO mixture.

Impact of water drops onto the junction of a hydrophobic texture and a hydrophilic smooth surface

Wettability gradient surfaces play a significant role in control and manipulation of liquid drops. The present work deals with the analysis of water drops impacting onto the junction line between hydrophobic texture and hydrophilic smooth portions of a dual-textured substrate made using stainless steel material. The hydrophobic textured portion of the substrate comprised of unidirectional parallel groove-like and pillar-like structures of uniform dimensions. A high-speed video camera recorded the spreading and receding dynamics of impacting drops. The drop impact dynamics during the early inertia driven impact regime remains unaffected by the dual-texture feature of the substrate. A larger retraction speed of drop liquid observed on the hydrophobic portion of the substrate during the impact of low velocity drops makes the drop liquid on the higher wettability portion to advance further (secondary drop spreading). The net horizontal drop velocity towards the hydrophilic portion of the dual-textured substrate decreases with increasing drop impact velocity. The available experimental results suggest that the movement of bulk drop liquid away from the impact point during drop impact on the dual-textured substrate is larger for the impact of low inertia drops. (C) 2010 Elsevier B.V. All rights reserved.

Studies in biogas technology. Part IV. A novel biogas plant incorporating a solar water-heater and solar still

A reduction in the heat losses from the top of the gas holder of a biogas plant has been achieved by the simple device of a transparent cover. The heat losses thus prevented have been deployed to heat a water pond formed on the roof of the gas holder. This solar-heated water is mixed with the organic input for ‘ hot-charging ’ of the biogas plant. A thermal analysis of such a solar water-heater ‘ piggy-backing ’ on the gas holder of a biogas plant has been carried out.To test whether the advantages indicated by the thermal analysis can be realised in practice, a biogas plant of the ASTRA design was modified to incorporate a roof-top solar water-heater. The operation of such a modified plant, even under ‘ worst case ’ onditions, shows a significant improvement in the gas yield compared to the unmodified plant. Hence, the innovation reported here may lead to drastic reductions in the sizes and therefore costs of biogas plants. By making the transparent cover assume a tent-shape, the roof-top solar heater can serve the additional function of a solar still to yield distilled water. The biogas plant-cum-solar water-heater-cum-solar still described here is an example of a spatially integrated hybrid device which is extremely cost-effective.

Studies in biogas technology. Part I. Performance of a conventional biogas plant

This paper gives an account of a conventional 5.66 m3/day (200 cubic ft/day) biogas plant which has been instrumented, operated and monitored for 2 1/2 years. The observations regarding input to the plant, sludge and biogas outputs, and conditions inside the digester, have been described. Three salient features stand out. First, the observed average daily gas yield is much less than the rated capacity of the plant. Secondly, the plants show ease of operation and a very slow response to reductions and cessations of dung supply. Thirdly, the unexpectedly marked uniformity of density and temperature inside the digester indicates the almost complete absence of the stratification which is widely believed to take place; hence, biogas plants may be treated as isothermal, ‘ uniform ’ density, most probably imperfectly mixed, fed-batch reactors operating at the mean ambient temperature and the density of water.

Sonochemical synthesis of Ce1-xFexO2-delta (0 <= x <= 0.45) and Ce0.65Fe0.33Pd0.02O2-delta nanocrystallites: oxygen storage material, CO oxidation and water gas shift catalyst

Nanocrystalline Ce1-xFexO2-delta (0 <= x <= 0.45) and Ce0.65Fe0.33Pd0.02O2-delta of similar to 4 nm sizes were synthesized by a sonochemical method using diethyletriamine (DETA) as a complexing agent. Compounds were characterized by powder X-ray diffraction (XRD), X-ray photo-electron spectroscopy (XPS) and transmission electron microscopy (TEM). Ce1-xFexO2-delta (0 <= x <= 0.45) and Ce0.65Fe0.33Pd0.02O2-delta crystallize in fluorite structure where Fe is in +3, Ce is in +4 and Pd is in +2 oxidation state. Due to substitution of smaller Fe3+ ion in CeO2, lattice oxygen is activated and 33% Fe substituted CeO2 i.e. Ce0.67Fe0.33O1.835 reversibly releases 0.31O] up to 600 degrees C which is higher or comparable to the oxygen storage capacity of CeO2-ZrO2 based solid solutions (Catal. Today 2002, 74, 225-234). Due to interaction of redox potentials of Pd2+/0(0.89 V) and Fe3+/2+ (0.77 V) with Ce4+/3+ (1.61 V), Pd ion accelerates the electron transfer from Fe2+ to Ce4+ in Ce0.65Fe0.33Pd0.02O1.815, making it a high oxygen storage material as well as a highly active catalyst for CO oxidation and water gas shift reaction. The activation energy for CO oxidation with Ce0.65Fe0.33Pd0.02O1.815 is found to be as low as 38 kJ mol(-1). Ce0.67Fe0.33O1.835 and Ce0.65Fe0.33Pd0.02O1.815 have also shown high activity for the water gas shift reaction. CO conversion to CO2 is 100% H-2 specific with these catalysts and conversion rate was found to be as high 27.2 mu moles g(-1) s(-1) and the activation energy was found to be 46.4 kJ mol(-1) for Ce0.65Fe0.33Pd0.02O1.815.

Ions in water: Role of attractive interactions in size dependent diffusivity maximum

A molecular dynamics study of model ions in water is reported. The van der Waals diameter of both the cations and anions is varied. We have carried out two sets of simulations-with and without dispersion interaction-between the ion and water. Self-diffusivity of the ions exhibits an anomalous maximum as a function of the van der Waals diameter for both these sets. This existence of a maximum in self-diffusivity when there is no dispersion interaction between the ion and the water is attributed to the attractive term from electrostatic interactions. Detailed analysis of this effect shows that the solvent shell is more strongly defined in the presence of dispersion interactions. A smaller ion exhibits biexponential decay while a single exponential decay is seen for the ion with maximum diffusivity in the self-part of the intermediate scattering function. The solvent structure around the ion appears to determine much of the dynamics of the ion. Interesting trends are seen in the activation energies and these can be understood in terms of the levitation effect. (C) 2010 American Institute of Physics. doi:10.1063/1.3481656]

A simple n-state model for water

A simple n-state configurational excitation model which takes into account the presence of weakly connected pentamer units in liquid water is proposed. The model has features of both the “continuum” and “mixture” models. Calculations based on this model satisfactorily account for the important, diagnostic thermodynamic properties of water such as the density maximum, fraction of monomers and so on.