Palladium(II) complexes of aliphatic amines and their oxidation by chloramine‐T in perchloric acid medium

The formation of palladium(II) complexes with aliphatic amines and their oxidation by chloramine‐T in perchloric acid medium has been studied. The spectrophotometric studies showed the formation of 1:1 and 1:2 complexes between palladium(II) and amine in absence of HClO₄. An increase in [HClO₄] in reaction mixture suppresses the complex formation and in presence of [HClO₄] ～10^?3 mol dm^?3 only a 1:1 complex between palladium(II) and amine has been observed. The effect of Cl^? on the complex formation has also been studied. Palladium(II)‐catalyzed oxidation of these amines by chloramine‐T showed a first‐order dependence of rate with respect to each—oxidant, substrate, catalyst, and H⁺. The mechanism consistent with kinetic data for the oxidation process has been proposed in absence as well as in presence of initial [Cl^?]. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 603–612, 2002     

Platinum(IV) complexes of reducing sugars in an alkaline medium and their resistance to reaction with N-bromosuccinimide. A kinetic study

Spectrophotometric studies support the formation of { Pt^IV–S} (where S = glucose, galactose and fructose) complexes in an alkaline medium. The resistance of these complexes to reaction with N-bromosuccinimide (NBS) has been observed. The kinetic data also support the formation of { Pt^IV –S} complexes.     

Photocatalytic CdSe QDs-decorated ZnO nanotubes: an effective photoelectrode for splitting water

Arrays of ZnO nanorods (NRs) were successfully converted into nanotubes (NTs), used as photoelectrodes in photoelectrochemical (PEC) cells after their sensitization with CdSe quantum dots (QDs) and a strong correlation between the PEC performance and geometrical structure of ZnO NTs@CdSe(QDs) and ZnO NRs@CdSe(QDs) was established under the same conditions.     

Inhibition of TX‐100 on the Rate of Hexacyanoferrate(III) Oxidation of Reducing Sugars: A Kinetic Study

An inhibition effect of nonionic micelles (polyoxyethylene (10) octyl phenol, commonly known as TX‐100) on the rate of oxidation of the reducing sugars, fructose, glucose, and maltose by alkaline hexacyanoferrate(III) has been observed. The kinetic data support a 1:1 association/binding between substrate and micelles. The binding constant and free energy transfer from water to micelle have been determined.     

Solving Navier–Stokes equation for flow past cylinders using single-block structured and overset grids

Many complex fluid motions are driven by physical processes of instability, transition and turbulence dependent upon nonlinear mechanisms. Here, we solve the flow past cylinder(s) using single-block structured and overset grids by computing Navier–Stokes equation in two-dimensions. The suitability of a compact scheme in discretizing convection and diffusion terms are investigated first by looking at relevant numerical properties. Also, for the overset grid method, one of the methods is identified that shows the best results in minimizing interpolation error at sub-domain boundaries for an analytical test function. We provide extensive comparisons with experimental and other computational results for flow past a single cylinder, utilizing both single-block structured and Chimera or overset grids. Apart from showing instability of this flow calculated by these methods, we also compare the computed vorticity and velocity data using these two grids by employing the proper orthogonal decomposition (POD). We have analyzed and developed an overset grid method with compact scheme that does not need any filtering to control error. This has been ascertained by performing POD analysis. To show that the developed method is capable of handling complex geometries, we have computed flow past two cylinders in side-by-side arrangement. Results obtained capture the known flow characteristics for this arrangement well using relatively fewer number of grid points.     

Hydrotropic Enhancement of Rate of the Browning Reaction; A Kinetic Study

The rate of a nonenzymatic browning reaction, that is, the reaction between reducing sugar and amino acid(commonly known as Millard reaction) is strongly enhanced in the presence of a common hydrotrope viz. sodium benzoate or sodium salicylate even below its minimal hydrotropic concentration (MHC). The effect of hydrotrope on the rate has been studied in four systems taking combination of different reducing sugars (glucose and fructose) and amino acids (glycine and alanine) in alkaline conditions. The kinetic data support the formation of the mixed aggregation between the hydrotrope and the reactants. The kinetic rate law consistent with experimental results has been derived on the basis of the proposed mechanism.     

Inhibition Effect of {Cationic Surfactant-Ascorbic Acid} Premicellar Aggregation on the Rate of Hexacyanoferrate(III) Oxidation of Ascorbic Acid: A Kinetic Study

The kinetics of oxidation of ascorbic acid by acidic hexacyanoferrate(III) have been investigated in presence of cationic surfactant viz. cetyltrimethylammonium bromide (CTAB). An inhibition effect of CTAB (below its critical micelle concentration) on the rate of oxidation has been observed. The spectrophotometric and kinetic data support a 1:1 premicellar association between substrate and surfactant. A mechanism has been proposed and a rate law consistent with kinetic results has been derived.     

Antagonism in (conventional anionic–gemini anionic) mixed micelle catalyzed oxidation of D‐fructose by alkaline chloramine‐T: A kinetic study

The catalytic effect of individual conventional anionic surfactant, namely, sodium lauryl sulfate (NaLS), anionic gemini surfactant, namely, sodium salt of bis(1‐dodecenyl succinamic acid) (NaBDS), and mixed surfactant (NaLS + NaBDS) on the rate of oxidation of D ‐fructose by alkaline chloramine‐T has been investigated. The reaction always showed a first‐order dependence of rate with respect to each fructose, alkali, and chloramine‐T. The rate was proportional to (k′+k″ [surfactant]), where k′ and k″ are the rate constants in the absence and presence of the surfactant, respectively. The binding parameters have been evaluated. The observed catalytic effect of mixed micelle on the rate of oxidation was always less than the algebraic sum of the catalytic effect of two surfactants when they were taken separately, suggesting an antagonism (negative synergism) in mixed micelle. The antagonism has also been confirmed by determining critical micelle concentration and interaction parameter (β^m) of mixed micelle under the experimental conditions of kinetics, that is, in alkaline medium. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 123–132, 2009     

Revision of the structure of the compound obtained by the reaction of 2-hydrazino-4-methylquinoline and acetylacetone

Condensation of 2-hydrazino-4-methylquinoline (1) and acetylacetone gives a compoundA, which has the structure of 3,5-dimethyl-1-(4-methylquinolino)-pyrazole (2) and not of 4-methylquinolino-(2,3—c)-3,5-dimethyl-1H-1,2-diazepine (3) assigned earlier. The structure2 was confirmed on the basis of¹H-NMR,¹³C-NMR, IR spectral data and its unambiguous synthesis.

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Revision der Struktur einer Verbindung aus der Reaktion von 2-Hydrazino-4-methylchinolin und Acetylaceton

Zusammenfassung Die Kondensation von 2-Hydrazino-4-methylchinolin (1) mit Acetylaceton ergibt eine Verbindung mit der Struktur eines 3,5-Dimethyl-1-(4-methylchinolin)pyrazols (2) und nicht eines 4-Methylchinolino-(2,3—c)-3,5-dimethyl-1H-1,2-diazepins (3) gemäß einer früheren Zuordnung. Die Struktur von2 wurde auf Grund von¹H-NMR,¹³C-NMR, IR und einer eindeutigen Synthese bewiesen.