Kinetics of Reduction of Some Surfactant-Cobalt(III) Complexes by Iron(II)

The electron transfer kinetics of the reaction between the surfactant-cobalt(III) complex ions, cis-[Co(en)₂(C₁₂H₂₅NH₂)₂]³⁺, cis-α-[Co(trien)(C₁₂H₂₅NH₂)₂]³⁺(en:ethylenediamine, trien:triethylenetetramine, C₁₂H₂₅NH₂ : dodecylamine) by iron(II) in aqueous solution was studied at 298, 303, 308 K by spectrophotometry method under pseudo-first-order conditions using an excess of the reductant in self-micelles formed by the oxidant, cobalt(III) complex molecules, themselves. The rate constant of the electron transfer reaction depends on the initial concentration of the surfactant cobalt(III) complexes. ΔS^# also varies with initial concentration of the surfactant cobalt(III) complexes. By assuming outer-sphere mechanism, the results have been explained based on the presence of aggregated structures containing cobalt(III) complexes at the surface of the self-micelles formed by the surfactant cobalt(III) complexes in the reaction medium. The rate constant of each complex increases with initial concentration of one of the reactants surfactant-cobalt(III) complex, which shows that self micelles formed by surfactant-cobalt(III) complex itself has much influence on these reactions. The electron transfer reaction of the surfactant-cobalt(III) complexes was also carried out in a medium of various concentrations of β-cyclodextrin. β-cyclodextrin retarded the rate of the reaction.     

Investigation of structural and magnetic properties of nanocrystalline manganese substituted lithium ferrites

Nanocrystalline manganese substituted lithium ferrites Li_0.5Fe_2.5−xMn_xO₄ (2.5≤x≥0) were prepared by sol-gel auto-combustion method. X-ray diffraction patterns revealed that as the concentration of manganese increased, the cubic phase changed to tetragonal. Magnetic properties were measured by hysteresis loop tracer technique. All the compositions indicated ferrimagnetic nature. The surface morphology of all the samples was studied by using scanning and transmission electron microscopy. The substitution of manganese ions in the lattice affected the structural as well as magnetic properties of spinels.     

Temperature programmed reduction studies of spillover effect in Pd impregnated metal oxide catalysts

Temperature programmed hydrogen reduction studies have been carried out for SnO₂ and Ce-Sn mixed oxides with and without Pd metal impregnation, to demonstrate the existence of spillover of hydrogen from Pd metal centers to support oxides. TPR pattern of SnO₂ showed a main peak at 973 K indicating the bulk reduction of this sample. In Pd metal impregnated sample, the bulk reduction peak shifts to lower temperature (923 K) due to the spillover of activated hydrogen from Pd metal to SnO₂ at relatively lower temperatures and its subsequent reaction with SnO₂. For Pd impregnated Ce-Sn mixed oxide samples also, a similar effect or an enhanced reduction was observed indicating the spillover effect of hydrogen. These results have been further confirmed from ¹¹⁹Sn Mössbauer spectroscopic measurements carried out for some representative samples of SnO₂ and Pd/SnO₂ heated in hydrogen flow up to a temperature of 473 K. The value of Sn²⁺/(Sn₄₊+Sn₂₊) ratio was found to be significantly higher for Pd impregnated sample. Both these observations provide direct evidence for the existence of spillover effect of hydrogen taking place in the metal impregnated samples.     

Density functional theory study of ω phase in steel with varied alloying elements

The presence of a long-abandoned hexagonal omega (ω) phase in steel samples is recently gaining momentum owing to the advances in transmission electron microscopy (TEM) measurements, even though it is already reported in other transition-metal alloys. The stabilization of this metastable phase is mainly investigated in presence of C, even though the formation of the ω phase is attributed to the combined effect of many factors, one among which is the enrichment of solute elements such as Al, Mn, Si, C, and Cr in the nanometer-sized regimes. The present study investigates the effect of the above alloying elements in ω-Fe using density functional theory (DFT) calculations. It is seen that the magnetic states of the atoms play a major role in the stability of ω-Fe. Cohesive energy calculations show that the alloying elements affect the energetics and stabilization of ω-Fe. Further, density of states calculations reveal the variation in d-band occupancy in the presence of alloying elements, which in turn affects the cohesive energy. Phonon band structure calculations show that only ω-Fe with substitutional C shows positive frequencies and hence possess thermodynamic stability. Finally, we confirm the existence of ω-Fe using TEM measurements of a steel sample containing the same alloying elements. Our results can shed light on the stabilization of the ω in other transition-metal alloys as well, in the presence of minor alloying elements.     

Enhanced hydrogen generation by particles during sonochemical decomposition of water

A novel effect of any oxide particle/intermetallics enhancing hydrogen generation from water as compared to water alone when subjected to ultrasonic irradiation is reported here. Addition of methanol to water or decrease in particle size also improved the hydrogen yield. Hydrogen generation from water was further enhanced by the presence of both methanol and particles in water.     

Study on visible luminescence of the Tm3 +: 1D2 → 3 F4 emission state in lead borate titanate aluminumfluoride glasses

This paper reports the visible luminescence properties of ¹D₂ state of Tm^3 + -doped lead borate titanate aluminumfluoride (LBTAFTm) glasses. The absorption and luminescence was analyzed within the frame work of Judd-Ofelt model. The reliability of J-O intensity parameters obtained from the experimental oscillator strengths have satisfactorily been correlated with the calculated oscillator strengths with small r.m.s deviation of ± 0.12 × 10^-6 by the least square fit analysis. Upon 359 nm excitation, the luminescence spectra show only one emission band at 458 nm (blue) corresponding to the ¹D₂ → ³ F₄ transition in the spectral region 400–500 nm. No luminescence quenching has been observed with the increase of Tm^3 + concentration. The decay profiles of the ¹D₂ level have shown single-exponential nature for all the concentrations and the decay times were found to decrease with the increase of concentration. The stimulated emission cross-section (σ_e) for the observed emission transition has also been computed. The large quantum efficiency (η) of the ¹D₂ level suggests the utility of LBTAFTm glass as a potential host for optical device applications at 458 nm emission wavelength.     

Synthesis of Ferrocene 1,3-Derivatives by Distal C−H Activation**

The third position of cyclopentadienyl ring of a monosubstituted ferrocene has remained as an inaccessible chemical space for direct functionalization. Until recently, functionalizing the C(3)-position while bypassing the predominantly active C(2)-position is the most challenging task. Herein, we report a distal C−H functionalization of monosubstituted ferrocenes using an easily removable directing group with precise site-selectivity, under a Pd^II/ mono-N-protected amino-acid ligand catalytic system. The robust synthetic protocol leads to the synthesis of ferrocene 1,3-derivatives with broad scope in olefins while functionalizing ferrocenyl methylamine in moderate to good yields via a highly strained ferrocene appended 12-membered palladacycle intermediate.