Acidity / basicity and electron donor properties and catalytic activity of sulphated titania

The surface acidity/ basicity of TiO2 (rutile) and its sulphate modified form have been determined by titration method using Hammett indicators after activation at different temperatures. The electron donating properties of these oxides are also studied from the adsorption of electron acceptors of different electron affinity values. The data have been correlated with the catalytic activity of these oxides towards esterification of acetic acid using n-butanol, reduction of cyclohexanone in isopropanol and oxidation of cyclohexanol in benzophenone. Catalytic activity for esterification and oxidation reaction parallels the acidity while that for reduction reaction parallels the basicity of these oxides.

Basicity and electron donor properties of lanthanum oxide and its mixed oxides with alumina

The electron donating properties of La2O3 activated at 300, 500 and 800·C and its mixed oxides with alumina are reported from the studies on adsorption of electron acceptors of varying electron affinity on La203. The electron acceptors with their electron affinity values given in parenthesis are: 7,7,8,8-tetracyanoquinodimethane (2.84 eV), 2,3,5,6-tetrachloro-I,4-benzoquinone (2.40 eV) and p-dinitrobenzene(l.77eV). The basicity of the oxide has been determined by titration with n-butylamine and Ho.max values are reported. The limit of electron transfer from the oxide to the electron acceptor is between 2.40 and 1.77 eV. It is observed that La203 promotes the surface electron properties of alumina without changing its limit of electron transfer.

Electron donor sites on Y2O3 catalyst as a function of the activation temperature

Cochin University of Science and Technology

Acid-base, electron-donating and magnetic properties of Nd2O3 and its mixed oxides with alumina catalysts

The electron donor properties of Nd2O3 activated at 300, 500 and 800°C were investigated through studies on the adsorption of electron acceptors of various electron affinities - 7, 7, 8,8-tetracyanoquinodimethane (2.84 eV). 2, 3, 5, 6-tetrachloro-l , 4-benzoquinone (2.40 eV). p-dinitrobenzene (1.77 eV), and m-dinitrobenzene (1.26 eV) in solvents acetonitrile and 1, 4-dioxan. The extent of electron transfer during adsorption has been found from magnetic measurements and electronic spectral data. The corresponding data on mixed oxides of neodymium and aluminium are reported for various. compositions. The acid-base properties of catalysts were also determined using a set of Hammett indicators.

Electron donor strength of rare earth oxides

The adsorption of electron acceptors, viz.,7,7,8,8-tetracyanoquinodimethane(TCNQ), 2,3,5,6-tetrachloro-p- benzoquinone (chloranil) and p-dinitrobenzene (PDNB) on the surface of three rare earth oxides Y2O3, Nd203 and Pr6O11 has been studied in acetonitrile and dioxan. From the radical concentration on the surface determined using ESR spectral data, the electron donor strength of the rare earth oxides are reported.

Solid acid-catalyzed dehydration/Beckmann rearrangement of aldoximes: towards high atom efficiency green processes

Rare earth metal ion exchanged (La3+, Ce3+, RE3+) KFAU-Y zeolites were prepared by simple ion-exchange methods and have been characterized using different physico-chemical techniques. In this paper a novel application of solid acid catalysts in the dehydration/ Beckmann rearrangement of aldoximes; benzaldoxime and 4-methoxybenzaldoxime is reported. Dehydration/Beckmann rearrangement reactions of benzaldoxime and 4-methoxybenzaldoxime is carried out in a continuous down flow reactor at 473K. 4-Methoxybenzaldoxime gave both Beckmann rearrangement product (4-methoxyphenylformamide) and dehydration product (4-methoxybenzonitrile) in high overall yields. The difference in behavior of the aldoximes is explained in terms of electronic effects. The production of benzonitrile was near quantitative under heterogeneous reaction conditions. The optimal protocol allows nitriles to be synthesized in good yields through the dehydration of aldoximes. Time on stream studies show a fast decline in the activity of the catalyst due to neutralization of acid sites by the basic reactant and product molecules.

Surface Electron Donor Properties of Dy2O3,Y2O3 and Their Mixed Oxides with Alumina Catalyst

The limit of electron transfer in electron affinity from the oxide surface to the electron acceptor (EA) are reported from the adsorption of EA on DY203, mixed oxides of DY203 with alumina and mixed oxides of Y203 with y-alumina. The extent of electron transfer is understood from magnetic measurements.

Electron-donating, acid-base, and magnetic properties of samaria catalyst

The electron-donor properties of Sm2O3 activated at 300, 500, and 800°C are reported from studies on the adsorption of electron acceptors of various electron affinities (electron affinity values in eV are given in parentheses): 7,7,8,8-tetracyanoquino-dimethane (2.84), 2,3,5,6-tetrachloro-1,4-benzoquinone (2.40), p-dinitrobenzene (1.77), and m-dinitrobenzene (1.26) in acetonitrile and 1,4-dioxane. The extent of electron transfer during the adsorption was determined from magnetic measurements. The acid-base properties of Sm2O3 at different activation temperatures are reported using a set of Hammett indicators. Electron donor-acceptor interactions at interfaces are important in elucidating the adhesion forces.

Structural Characterization and Non-linear Optical Properties of Metal Complexes of Some Donor-Acceptor Substituted N-salicylidene-N' -aroylhydrazine Ligands

The present work deals with the complexation of Schiff bases of aroylhydrazines with various transition metal ions. The hydrazone systems selected for study have long 7I:-delocalized chain in the ligand molecule itself, which get intensified due to metal-to-ligand or ligand-to-metal charge transfer excitations upon coordination. Complexation with metal ions like copper, nickel, cobalt, manganese, iron, zinc and cadmium are tried. Various spectral techniques are employed for characterization. The structures of some complexes have been well established by single crystal X-ray diffraction studies. The nonIinaer optical studies of the ligands and complexes synthesized have been studied by hyper-Rayleigh scattering technique.The work is presented in seven chapters and the last one deals with summary and conclusion. One of the hydrazone system selected for study proved that it could give rise to polymeric metal complexes. Some of the copper, nickel, zinc and cadmium complexes showed non-linear optical activity. The NLO studies of manganese and iron showed negative result, may be due to the inversion centre of symmetry within the molecular lattice.

Phenylethynylarene Based Donor-Acceptor Systems: Design, Synthesis and Photophysical Studies

This thesis Entitled phenylethynylarene based Donor-Acceptor systems:Desigh,Synthesis and Photophysical studies. A strategy for the design of donor-acceptor dyads, wherein decay of the charge separated (CS) state to low lying local triplet levels could possibly be prevented, is proposed. In order to examine this strategy, a linked donor-acceptor dyad BPEPPT with bis(phenylethYlly/)pyrene (BPEP) as the light absorber and acceptor and phenothiazine (PT) as donor was designed and photoinduced electron transfer in the dyad investigated. Absorption spectra of the dyad can be obtained by adding contributions due 10 the BPEP and PT moieties indicating that the constituents do not interact in the ground stale. Fluorescence of the BPEP moiety was efficiently quenched by the PT donor and this was attributed to electron lransfer from PT to BPEP. Picosecond transient absorption studies suggested formation of a charge separated state directly from the singlet excited state of BPEP. Nanosecond flash photolysis experiments gave long-ived transient absorptions assignable to PT radical cation and BPEP radical anion. These assignments were confirmed by oxygen quenching studies and secondary electron transfer experiments. Based on the available data, energy level diagram for BPEP-PT was constructed. The long lifetime of the charge separated state was attributed to the inverted region effects. The CS state did not undergo decay to low lying BPEP triplet indicating the success of our strategy

Some problems in set topology relating group of homeomorphisms and order

In this thesis we investigate some problems in set theoretical topology related to the concepts of the group of homeomorphisms and order. Many problems considered are directly or indirectly related to the concept of the group of homeomorphisms of a topological space onto itself. Order theoretic methods are used extensively. Chapter-l deals with the group of homeomorphisms. This concept has been investigated by several authors for many years from different angles. It was observed that nonhomeomorphic topological spaces can have isomorphic groups of homeomorphisms. Many problems relating the topological properties of a space and the algebraic properties of its group of homeomorphisms were investigated. The group of isomorphisms of several algebraic, geometric, order theoretic and topological structures had also been investigated. A related concept of the semigroup of continuous functions of a topological space also received attention

Some Lattice Problems In Fuzzy Set Theory And Fuzzy Topology

It is believed that every fuzzy generalization should be formulated in such a way that it contain the ordinary set theoretic notion as a special case. Therefore the definition of fuzzy topology in the line of C.L.CHANG E9] with an arbitrary complete and distributive lattice as the membership set is taken. Almost all the results proved and presented in this thesis can, in a sense, be called generalizations of corresponding results in ordinary set theory and set topology. However the tools and the methods have to be in many of the cases, new. Here an attempt is made to solve the problem of complementation in the lattice of fuzzy topologies on a set. It is proved that in general, the lattice of fuzzy topologies is not complemented. Complements of some fuzzy topologies are found out. It is observed that (L,X) is not uniquely complemented. However, a complete analysis of the problem of complementation in the lattice of fuzzy topologies is yet to be found out

Crystal Structures and Spectral Aspects of Mixed Ligand Transition Metal Chelates Derived from Aldehyde based ONS Donor Thiosemicarbazones

Thiosemicarbazones have emerged as an important class of ligands over a period of time, for a variety of reasons, such as variable donor properties, structural diversity and biological applications. Interesting as the coordination chemistry may be, the driving force for the study of these ligands has undoubtedly been their biological properties and the majority of the 3000 or so publications on thiosemicarbazones since 2000 have alluded to this feature. Thiosemicarbazones with potential donor atoms in their structural skeleton fascinate coordination chemists with their versatile chelating behavior. The thiosemicarbazones of aromatic aldehydes and ketones form stable chelates with transition metal cations by utilizing both their sulfur and azomethine nitrogen as donor atoms. They have been shown to possess a diverse range of biological activities including anticancer, antitumor, antibacterial, antiviral, antimalarial and antifungal properties owing to their ability to diffuse through the semipermeable membrane of the cell lines. The enhanced effect may be attributed to the increased lipophilicity of the metal complexes compared to the ligand alone.

Synthesis, characterization and physiochemical information, along with antimicrobial studies of some metal complexes derived from an ON donor semicarbazone ligand

Eight new transition metal complexes of benzaldehyde-N(4)–phenylsemicarbazone have been synthesized and characterized by elemental analyses, molar conductance, electronic and infrared spectral studies. In all the complexes, the semicarbazone is coordinated as neutral bidentate ligand. 1H NMR spectrum of [Zn(HL)2(OAc)2] shows that there is no enolisation of the ligand in the complex. The magnetic susceptibility measurements indicate that Cr(III), Mn(II), Fe(III), Co(II) and Cu(II) complexes are paramagnetic and Ni(II) is diamagnetic. The EPR spectrum of [Mn(HL)2(OAc)2] in DMF solution at 77K shows hyperfine sextet with low intensity forbidden lines lying between each of the two main hyperfine lines. The g values calculated for the [Cu(HL)2SO4] complex in frozen DMF, indicate the presence of unpaired electron in the dx2−y2 orbital. The metal ligand bonding parameters evaluated showed strong in-plane bonding and in-plane bonding. The ligand and complexes were screened for their possible antimicrobial activities.

Synthesis and spectral investigations of vanadium(IV/V) complexes derived from an ONS donor thiosemicarbazone ligand

Four oxovanadium and one dioxovanadium complex with 2-hydroxyacetophenone N(4)- phenylthiosemicarbazone (H2L) which are represented as [VOLphen]·2H2O (1), [VOLbipy] (2), [VOLdmbipy] (3), [VOL]2 (4) and [VO2HL]·CH3OH (5) have been synthesized and characterized by elemental analyses, electronic, infrared and EPR spectral techniques. In all the complexes 1–4 the ligand coordinates through phenolic oxygen, azomethine nitrogen and thiolate sulfur. But in complex [VO2HL]·CH3OH, coordination takes place in thione form instead of thiolate sulfur. All the complexes except [VO2HL]·CH3OH are EPR active due to the presence of an unpaired electron. In frozen DMF at 77 K, all the oxovanadium(IV) complexes show axial anisotropy with two sets of eight line patterns