Kinetics and mechanism of anodic oxidation of chlorate ion to perchlorate ion on lead dioxide electrodes

The kinetics and mechanism of anodic oxidation of chlorate ion to perchlorate ion on titanium-substrate lead dioxide electrodes have been investigated experimentally and theoretically. It has been demonstrated that the ionic strength of the solution has a marked effect on the rate of perchlorate formation, whereas the pH of the solution does not influence the reaction rate. Experimental data have also been obtained on the dependence of the reaction rate on the concentration of chlorate ion in the solution at constant ionic strength. With these data, diagnostic kinetic criteria have been deduced and compared with corresponding quantities predicted for various possible mechanisms including double layer effects on electrode kinetics. It has thus been shown that the most probable mechanisms for anodic chlorate oxidation on lead dioxide anodes involve the discharge of a water molecule in a one-electron transfer step to give an adsorbed hydroxyl radical as the rate-determining step for the overall reaction.

An investigation of solid adamantane by a modified isothermal-isobaric ensemble Monte Carlo simulation

Isothermal-isobaric ensemble Monte Carlo simulation studies of adamantane have been carried out at different temperatures. Thermodynamic properties and radial distribution functions calculated by employing a simple potential model based on sitesite interactions show good agreement with experiment and suggest that the solid is orientationally disordered at high temperatures.

Adsorption of CO and N2 on modified transition-metal surfaces

Electron spectroscopic studies clearly demonstrate that modification of the surfaces of Mn, Fe and Ni metals by chlorine significantly decreases the strength of interaction between the metal and adsorbed molecules such as CO and N2. This is in contrast to the effect of electropositive additives such as Ba and Al which increase the adsorption bond strength significantly.

Anionic clay-Pt metal nanoparticle composite through intercalation of hexachloroplatinate in nickel zinc hydroxysalt

Nickel zinc hydroxysalt–Pt metal nanoparticle composite was prepared by intercalation of the anionic platinum complex, [PtCl6]2− in nickel zinc hydroxysalt through ion exchange reaction and subsequent reduction of the platinum complex by ethanol. Powder X-ray diffraction and microscopy studies indicate that the process of reduction of the platinum complex in the interlayer region of the anionic clay takes place topotactically without destroying the layers.

Ce1-xRuxO2-delta (x=0.05, 0.10): A New High Oxygen Storage Material and Pt, Pd-Free Three-Way Catalyst

Nanocrystalline Ce1-xRuxO2-delta (x = 0.05 and 0.10) of 8-10 nm sizes have been synthesized by hydrothermal method using melamine as complexing agent. Compounds have been characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray analysis (EDX) and their structures have been refined by the Rietveld method.The compounds crystallize in fluorite structure and the composition is Ce1-xRuxO2-x/2 where Ru is in +4 state and Ce is in mixed-valence (+3, +4) state. Substitution of Ru4+ ion in CeO2 activated the lattice oxygen. Ce1-xRuxO2-x/2 reversibly releases 0.22[O] and 0.42[O] for x = 0.05 and 0.10, respectively, which is higher than the maximumpossible OSC of 0.22 [O] observed for Ce0.50Zr0.50O2. Utilization of Higher OSC of Ce1-xRuxO2-delta (x = 0.05 and 0.10) is also reflected in terms of low-temperature CO oxidation with these catalysts, both in the presence and absence of feed oxygen. The Ru4+ ion acts as an active center for reducing molecules (CO, hydrocarbon ``HC'') and oxide ion vacancy acts as an active center for O-2 and NO, leading to low-temperature NO conversion to N-2. Thus due to Ru4+ ion, Ce1-xRuxO2-delta is not just a high oxygen storage material but also shows high activity toward CO, hydrocarbon ``HC'' oxidation, and NO reduction by CO at low temperature with high N-2 selectivity for three-way catalysis.

Oxides supported carbon air-electrodes for alkaline solution power devices

Porous carbon oxygen-reducing electrodes incorporated with perovskite oxide catalysts are reported. It has been possible to fabricate high-performance oxygen-reducing electrodes by introducing La0.5Sr0.5CoO3 and La0.99Sr0.01NiO3 with the activated coconut-shell charcoal; these electrodes could sustain load currents as high as 1 A cm−2 without serious degradation. A model to explain oxygen-reducing activity of these oxides has been proposed.

Solubilities of solids in supercritical fluids using dimensionally consistent modified solvate complex models

New dimensionally consistent modified solvate complex models are derived to correlate solubilities of solids in supercritical fluids both in the presence and absence of entrainers (cosolvents). These models are compared against the standard solvate complex models [J.Chrastil, J. Phys. Chem. 86 (1982) 3016-3021; J.C. Gonzalez, M.R.Vieytes, A.M. Botana, J.M. Vieites, L.M. Botana, J. Chromatogr. A 910 (2001) 119-125; Y. Adachi, B.C.Y. Lu, Fluid Phase Equilb. 14 (1983) 47-156; J.M. del Valle, J.M. Aguilera, Ind. Eng. Chem. Res. 27 (1988) 1551-1553] by correlating the solubilities of 13 binary and 12 ternary systems. Though the newly derived models are not significantly better than the standard models in predicting the solubilities, they are dimensionally consistent. (C) 2009 Elsevier B.V. All rights reserved.

Self-Assembly of Molecular Prisms via Pt-3 Organometallic Acceptors and a Pt-2 Organometallic Clip

The design and two-component [2 + 3] self-assembly of a series of new organometallic molecular prisms (3a-d) are described. Assemblies 3a,b incorporate 4,4',4'-tris[ethynyl-trans-Pt(PEt3)(2)]triphenylamine (1a) containing a Pt-ethynyl functionality as tritopic planar acceptor and organic ``clips'' 2a and 2b, respectively [where 2a = 1,3-bis(3-pyridyl)isophthalic amide; 2b= 1,3-bis(ethynyl-3-pyridyl)benzene]. In a complementary approach all organic tritopic planar donor ligand 2c [2c 4,4',4'-tris(4-pyridylethynyl)triphenylamine] was assembled with all organometallic ``clip'', 1,8-bis[{trans-Pt(PEt3) (2)(NO3)}ethynyl]anthracene (1b), to obtain prism 3c. A organometallic carbon-centered acceptor, 1,1,1- tris[4-{trans-Pt(PEt3)(2)(NO3)}ethynylphenyl]ethane (1c), has been prepared, and its prism derivative (3d) using an organic `clip'' is prepared. Assemblies (3a-d) were characterized by multinuclear NMR spectroscopy, electrospray ionization mass spectroscopy, and elemental analysis. 3a-d showed fluorescence behavior in solution, and quenching of fluorescence intensity (3a,3c-d) was noticed upon addition of TNT (2,4,6-trinitrotoluene), a common constituent of many commercial explosives. A thin film of the assembly 3d made by spin coating of a solution of 3 x 10(-5) M in DMF on it 1 cm(2) quartz plate showed fluorescence response to the vapor of TNT.

A Modified Heffron-Phillip's Model for The Design of Power System Stabilizers

In this paper a modified Heffron-Phillip's (K-constant) model is derived for the design of power system stabilizers. A knowledge of external system parameters, such as equivalent infinite bus voltage and external impedances or their equivalent estimated values is required for designing a conventional power system stabilizer. In the proposed method, information available at the secondary bus of the step-up transformer is used to set up a modified Heffron-Phillip's (ModHP) model. The PSS design based on this model utilizes signals available within the generating station. The efficacy of the proposed design technique and the performance of the stabilizer has been evaluated over a range of operating and system conditions. The simulation results have shown that the performance of the proposed stabilizer is comparable to that could be obtained by conventional design but without the need for the estimation and computation of external system parameters. The proposed design is thus well suited for practical applications to power system stabilization, including possibly the multi-machine applications where accurate system information is not readily available.

Modified current source inverter fed induction motor drive with reduced torque pulsations

A new technique for reducing the torque pulsations in a conventional current source inverter fed induction motor drive is presented. This does not attempt to improve the current waveforms, but modifies the airgap MMF directly. This is based on the use of a motor with two sets of balanced phase windings, with a 30 electrical degree phase difference between them, and each set being fed from a conventional current source inverter. The two inverters are further connected in series so that they can operate from the same current source. As a consequence of this arrangement, the voltage rating of the components of each inverter is reduced, along with reduced torque ripple. This scheme has been experimentally verified and compared with the performance of a conventional scheme.

Metabolism of structurally modified acyclic monoterpenes by Pseudomonas incognita

The ability of Pseudomonas incognita to metabolize some structurally modified acyclic monoterpenes was tested. The 6,7 double bond was found essential for these compounds to serve as a substrate for this organism, whereas the same was not true with the 1,2 double bond. Metabolism of dihydrolinalyl acetate by this strain yielded dihydrolinalool, dihydrolinalool-8-carboxylic acid, dihydrolinalyl acetate-8-carboxylic acid, and 4-acetoxy-4-methyl hexanoic acid. A cell-free extract prepared from dihydrolinalyl acetate grown cells transformed dihydrolinalyl acetate into dihydrolinalool and dihydrolinalool-8-carboxylic acid. Based on the identification of various metabolites isolated from the culture medium, and on growth and manometric studies carried out with the isolated metabolites as well as with related synthetic analogs, probable pathways for the biodegradation of dihydrolinalyl acetate are presented.

2-O-methyl-1-methyl adenosine: A new modified nucleoside in ragi (eleusine coracana ) tRNA

A new modified nucleoside 2-²-O-methyl-l-methyl adenosine has been found to be present in the tRNA of (eleusine coracana ) (ragi) seedlings. The sequence of the dinucleotide of which this modified nucleoside is a part suggests its presence in phenylalanine-tRNA. The structural implications of the presence of this new modification are discussed.

Modified Lu-Lee cryptosystem

A modified Lu-Lee cryptosystem is proposed which appears to be resistant to the cryptanalytic attacks on the original Lu-Lee scheme. The data expansion due to encryption is moderate, and the size of the public key is also quite small.

Layer-by-layer self-assembly of modified hyaluronic acid/chitosan based on hydrogen bonding

The fabrication of hydrogen bonded polymer self-assembly for drug delivery has been accomplished via layer-by-layer sequential assembly from aqueous solution. In this study, the self-assembly was constructed based on hydrogen bonding between DNA base (adenine and thymine) pairs substituted on the backbone of chitosan and hyaluronic acid. Chitosan was modified with adenine, whereas hyaluronic acid was modified with thymine. Subsequently, these two polymers were sequentially absorbed on flat substrate by taking advantage of interactions of DNA base pairs via hydrogen bonding. Interlayer hydrogen bonding of these two polymers produces stable multilayer film without using any cross-linking agent. Thin film formation on quartz substrate has been monitored with UV-vis spectra and an AFM study. Formation of multilayer hydrogen-bonded thin film has been further confirmed with SEM. Encapsulation and release behavior of the therapeutic drug from the multilayer thin film at different conditions has been illustrated using UV-vis spectra. Cell viability of modified polymers using MTT assay confirmed no cytotoxic effect.

Modified design procedure for a sparger reactor sequence

In an earlier communication[l] we have indicated a general graphical design procedure for a sequence of sparger reactors in which a second order liquid phase reaction proceeds in a stagewise fashion. The prediction of the reactant concentration in each stage and hence the conversion depended on a search procedure initiated along a straight line representing the mass balance equation at the given stage and drawn from the known feed stage located on the abscissa in a E-IU diagram for the given system.