Ce0.67Cr0.33O2.11: A New Low-Temperature O-2 Evolution Material and H-2 Generation Catalyst by Thermochemical Splitting of Water

Ce0.67Cr0.33O2.11 was synthesized by hydrothermal method using diethylenetriamine as complexing agent (Chem. Mater. 2008, 20, 7268). Ce0.67Cr0.33O2.11 being the only compound likes UO2+delta to have excess oxygen, it releases a large proportion of its lattice oxygen (0.167 M [O]/mole of compound) at relatively low temperature (465 degrees C) directly and it has been utilized for generation of H-2 by thermo-splitting of water. An almost stoichiometric amount of H-2 (0.152 M/Mole of compound) is generated at much lower temperature (65 degrees C). There is an almost comparable amount of oxygen release and hydrogen generation over this material at very low temperature comparedto other CeO2-MOx (Mn, Fe, Cu, and Ni) mixed-oxide solid solutions (O-2 evolution >= 1300 degrees C and H-2 generation at 1000 degrees C). The reversible nature of oxygen release and intake of this material is attributed to its fluorite Structure and coupling between the Ce4+/Ce3+ and Cr4+/6+/Cr3+ redox couples. Compound shows reversible oxygen release and intake by H2O absorption and subsequent hydrogen release to gain parent structure and hence this material can be utilized for generation of H-2 at very low temperature by thermo-chemical splitting of water.

Replacement of water on a steel substrate by a surrounding oil reservoir

With an objective to replace a water droplet from a steel surface by oil we study here the impact of injecting a hydrophilic/lipophilic surfactant into the droplet or into the surrounding oil reservoir. Contact angle goniometery, Grazing angle FTIR spectroscopy and Atomic force microscopy are used to record the oil/water interfacial tension, surface energetics of the substrate under the oil and water phases as well as the corresponding physical states of the substrates. Such energetics reflect the rate at which the excess surfactant molecules accumulate at the water/oil interface and desorb into the phases. The molecules diffuse into the substrate from the phases and build up specific molecular configurations which, with the interfacial tension, control the non-equilibrium progress of and the equilibrium status of the contact line. The study shows that the most efficient replacement of water by the surrounding oil happens when a surfactant is sparingly soluble in the supplier oil phase and highly soluble in the recipient water phase.

An acid method for the volumetric estimation of water-soluble dithiocarbamates

Dithiocarbamates have been estimated previously by reaction with a strong acid, the carbon disulfide evolved being converted into a xanthate and the latter estimated iodimetrically. In the present method, a water-soluble dithiocarbamate is reacted with a decinormal mineral acid and the excess acid is determined to compute the amount of dithiocarbamate present. This method is applicable for the determination of a dithiocarbamate in a mixture containing thiuram disulfide.

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.

Structural Transformations, Composition Anomalies and a Dramatic Collapse of Linear Polymer Chains in Dilute Ethanol-Water Mixtures

Water-ethanol mixtures exhibit many interesting anomalies, such as negative excess partial molar volume of ethanol, excess sound absorption coefficient at low concentrations, and positive deviation from Raoult's law for vapor pressure, to mention a few. These anomalies have been attributed to different, often contradictory origins, but a quantitative understanding is still lacking. We show by computer simulation and theoretical analyses that these anomalies arise from the sudden emergence of a bicontinuous phase that occurs at a relatively low ethanol concentration of x(eth) approximate to 0.06-0.10 (that amounts to a volume fraction of 0.17-0.26, which is a significant range!). The bicontinuous phase is formed by aggregation of ethanol molecules, resulting in a weak phase transition whose nature is elucidated. We find that the microheterogeneous structure of the mixture gives rise to a pronounced nonmonotonic composition dependence of local compressibility and nonmonotonic dependence in the peak value of the radial distribution function of ethyl groups. A multidimensional free energy surface of pair association is shown to provide a molecular explanation of the known negative excess partial volume of ethanol in terms of parallel orientation and hence better packing of the ethyl groups in the mixture due to hydrophobic interactions. The energy distribution of the ethanol molecules indicates additional energy decay channels that explain the excess sound attenuation coefficient in aqueous alcohol mixtures. We studied the dependence of the solvation of a linear polymer chain on the composition of the water-ethanol solvent. We find that there is a sudden collapse of the polymer at x(eth) approximate to 0.05-a phenomenon which we attribute to the formation of the microheterogeneous structures in the binary mixture at low ethanol concentrations. Together with recent single molecule pulling experiments, these results provide new insight into the behavior of polymer chain and foreign solutes, such as enzymes, in aqueous binary mixtures.

Preferential oxidation of CO on Ni/CeO2 catalysts in the presence of excess H-2 and CO2

Preferential oxidation of CO (CO-PROX) was carried out over Ni supported on CeO2 prepared by the co-precipitation method. The influence of metal loadings (2.5, 5 and 10 wt.% Ni) and the reaction conditions such as reaction temperature and feed composition on CO oxidation and oxidation selectivity were evaluated by using dry reformate gas. No other reactions like CO or CO2 methanation, coking, reverse water gas shift (RWGS) reaction is observed in the temperature range of 100-200 A degrees C on these catalysts. Hydrogen oxidation dominates over CO oxidation above the temperature of 200 A degrees C. An increase in oxygen leads to an increase in CO conversion but a simultaneous decrease in the O-2 selectivity. It has been noticed that 5 and 10 % Ni/CeO2 show better catalytic activity towards CO-PROX reaction. These catalysts were characterized by S-BET, XRD, TEM, XPS and H-2-TPR.

Instability in an amorphous In-Ga-Zn-O field effect transistor upon water exposure

The instability of an amorphous indium-gallium-zinc oxide (IGZO) field effect transistor is investigated upon water treatment. Electrical characteristics are measured before, immediately after and a few days after water treatment in ambient as well as in vacuum conditions. It is observed that after a few days of water exposure an IGZO field effect transistor (FET) shows relatively more stable behaviour as compared to before exposure. Transfer characteristics are found to shift negatively after immediate water exposure and in vacuum. More interestingly, after water exposure the off current is found to decrease by 1-2 orders of magnitude and remains stable even after 15 d of water exposure in ambient as well as in vacuum, whereas the on current more or less remains the same. An x-ray photoelectron spectroscopic study is carried out to investigate the qualitative and quantitative analysis of IGZO upon water exposure. The changes in the FET parameters are evaluated and attributed to the formation of excess oxygen vacancies and changes in the electronic structure of the IGZO bulk channel and at the IGZO/SiO2 interface, which can further lead to the formation of subgap states. An attempt is made to distinguish which parameters of the FET are affected by the changes in the electronic structure of the IGZO bulk channel and at the IGZO/SiO2 interface separately.

A water model study of the flow asymmetry inside a continuous slab casting mold

The work studies the extent of asymmetric flow in water models of continuous casting molds of two different configurations. In the molds where fluid is discharged through multiple holes at the bottom, the flow pattern in the lower portion depends on the size of the lower two recirculating domains. If they reach the mold bottom, the flow pattern in the lower portion is symmetrical about the central plane; otherwise, it is asymmetrical. On the other hand, in the molds where the fluid is discharged through the entire mold cross section, the flow pattern is always asymmetrical if the aspect ratio is 1:6.25 or more. The fluid jet swirls while emerging through the nozzle. The interaction of the swirling Jets with the wide sidewalls of the mold gives rise to asymmetrical flow inside the mold. In the molds with lower aspect ratios, where the jets do not touch the wide side walls, the flow pattern is symmetrical about the central plane.

Intermittent Dynamics, Stochastic Resonance and Dynamical Heterogeneity in Supercooled Liquid Water

Here we find through computer simulations and theoretical analysis that the low temperature thermodynamic anomalies of liquid water arises from the intermittent fluctuation between its high density and low density forms, consisting largely of 5-coordinated and 4-coordinated water molecules, respectively. The fluctuations exhibit strong dynamic heterogeneity (defined by the four point time correlation function), accompanied by a divergence like growth of the dynamic correlation length, of the type encountered in fragile supercooled liquids. The intermittency has been explained by invoking a two state model often employed to understand stochastic resonance, with the relevant periodic perturbation provided here by the fluctuation of the total volume of the system.

Liquefaction And Pore Water Pressure Generation In Sand - A Cyclic Strain Approach

This paper presents the results of laboratory investigation carried out on Ahmedabad sand on the liquefaction and pore water pressure generation during strain controled cyclic loading. Laboratory experiments were carried out on representative natural sand samples (base sand) collected from earthquake-affected area of Ahmedabad City of Gujarat State in India. A series of strain controled cyclic triaxial tests were carried out on isotropically compressed samples to study the influence of different parameters such as shear strain amplitude, initial effective confining pressure, relative density and percentage of non-plastic fines on the behavior of liquefaction and pore water pressure generation. It has been observed from the laboratory investigation that the potential for liquefaction of the sandy soils depends on the shear strain amplitude, initial relative density, initial effective confining pressure and non-plastic fines. In addition, an empirical relationship between pore pressure ratio and cycle ratio independent of the number of cycles of loading, relative density, confining pressure, amplitude of shear strain and non-plastic fines has been proposed.

An Integrated Assessment Of The Suitability Of Domestic Solar Still As A Viable Safe Water Technology For India

Improving access to safe drinking water can result in multi-dimensional impacts on people's livelihood. This has been aptly reflected in the Millennium Development Goals (MDG) as one of the major objectives. Despite the availability of diverse and complex set of technologies for water purification, pragmatic and cost-effective use of the same is impeding the use of available sources of water. Hence, in country like India simple low-energy technologies such as solar still are likely to succeed. Solar stills would suffice the basic minimum drinking water requirements of man. Solar stills use sunlight, to kill or inactivate many, if not all, of the pathogens found in water. This paper provides an integrated assessment of the suitability of domestic solar still as a viable safe water technology for India. Also an attempt has been made to critically assess the operational feasibility and costs incurred for using this technology in rural India.

Fuzzy optimization model for water quality management of a river system - Closure

A fuzzy waste-load allocation model, FWLAM, is developed for water quality management of a river system using fuzzy multiple-objective optimization. An important feature of this model is its capability to incorporate the aspirations and conflicting objectives of the pollution control agency and dischargers. The vagueness associated with specifying the water quality criteria and fraction removal levels is modeled in a fuzzy framework. The goals related to the pollution control agency and dischargers are expressed as fuzzy sets. The membership functions of these fuzzy sets are considered to represent the variation of satisfaction levels of the pollution control agency and dischargers in attaining their respective goals. Two formulations—namely, the MAX-MIN and MAX-BIAS formulations—are proposed for FWLAM. The MAX-MIN formulation maximizes the minimum satisfaction level in the system. The MAX-BIAS formulation maximizes a bias measure, giving a solution that favors the dischargers. Maximization of the bias measure attempts to keep the satisfaction levels of the dischargers away from the minimum satisfaction level and that of the pollution control agency close to the minimum satisfaction level. Most of the conventional water quality management models use waste treatment cost curves that are uncertain and nonlinear. Unlike such models, FWLAM avoids the use of cost curves. Further, the model provides the flexibility for the pollution control agency and dischargers to specify their aspirations independently.

Fuzzy Logic-Based Approaches in Water Resource System Modelling

Recent research in modelling uncertainty in water resource systems has highlighted the use of fuzzy logic-based approaches. A number of research contributions exist in the literature that deal with uncertainty in water resource systems including fuzziness, subjectivity, imprecision and lack of adequate data. This chapter presents a broad overview of the fuzzy logic-based approaches adopted in addressing uncertainty in water resource systems modelling. Applications of fuzzy rule-based systems and fuzzy optimisation are then discussed. Perspectives on the scope for further research are presented.

Consolidation Behavior of Soils

Based on Terzaghi's consolidation theory, percent of consolidation, U, versus the time factor, T, relationship for constant/linear excess pore water pressure distribution, it is possible to generate theoretical log10(H2/t) versus U curves where H is the length of the drainage path of a consolidating layer, and t is the time for different known values of the coefficient of consolidation, cν. A method has been developed wherein both the theoretical and experimental behavior of soils during consolidation can be simultaneously compared and studied on the same plot. The experimental log10(H2/t) versus U curves have been compared with the theoretical curves. The deviations of the experimental behavior from the theory are explained in terms of initial compression and secondary compression. Analysis of results indicates that the secondary compression essentially starts from about 60% consolidation. A simple procedure is presented for calculating the value of cv from the δ-t data using log10(H2/t) versus U plot.

Metal-Ion-Dependent Oxidative DNA Cleavage by Transition Metal Complexes of a New Water-Soluble Salen Derivative

A new water-soluble, salen [salen = bis(salicylidene) ethylenediamine]-based ligand, 3 was developed. Two of the metal complexes of this ligand, i.e., 3a, [Mn(III)] and 3b, [Ni(II)], in the presence of cooxidant magnesium monoperoxyphthalate (MMPP) cleaved plasmid DNA pTZ19R efficiently and rapidly at a concentration similar to 1 mu M. In contrast, under comparable conditions, other metal complexes 3c, [Cu(II)] or 3d, [Cr(III)] could not induce any significant DNA nicking. The findings with Ni(II) complex suggest that the DNA cleavage processes can be modulated by the disposition of charges around the ligand.