Chemical and electrochemical investigations of cobalt cyanide and ruthenium ammine complexes

Part I.

The stoichiometry and kinetics of the reaction between Co(CN₅H^3- and HgX₂ (X = CN, OH) have been investigated. The products of the reaction are two new complexes, [(NC)₅Co-HgX]^3- and [(NC)₅Co-Hg-Co(CN)₅]^6-, whose spectra are reported. The kinetic measurements produced a value for the forward rate constant of the reaction Co(CN)₅H^3- + OH^- k₁/k_-1 Co(CN)₅^4- +H₂O, k1 = (9.7 ± 0.8) x 10^-2 M^-1 sec^-1 at 24°C, and an equilibrium constant for the reaction K = 10^-6 M^-1.

Part II.

Unusually large and sharp "adsorption waves" appear in cyclic voltammograms of Co(CN)₅^3- and several cobalt(III) pentacyano complexes at stationary mercury electrodes. The nature of the adsorbed species and the reasons for the absence of the adsorption waves in polarograms taken with a d.m.e. have been examined. The data are compatible with the adsorption, in all cases, of a coordinatively unsaturated cobalt(II) complex, Co(CN)₄^2-, by means of a cobalt-mercury bond. When the resulting adsorbed complex is reduced, a series of subsequent chemical and electrode reactions is initiated in which three faradays of charge are consumed for each mole of adsorbed complex. The adsorption of the anionic complex strongly retards the reduction of other negatively charged complexes.

Part III.

A number of formal redox potentials for Ru^III (NH₃)₅L + e = Ru^II (NH₃)₅L and Ru^III(NH₃)₄L₂ + e = Ru^II (NH₃)₄L₂ (where L is various ligands) has been measured by cyclic voltammetry, potentiometry, and polarography and are discussed in terms of the properties of the ligands, such as π-accepting capability. Reduction of coordinated pyrazine in the complexes, Ru(NH₃)₅ Pz²⁺, cis- and trans-Ru(NH₃)₄Pz₂²⁺, on a mercury electrode has been observed. The behavior of this reduction in various acidity of the solution as well as the reoxidation of the reduction products are discussed.

Petrologia dos diabásios da região de Angra dos Reis, RJ

O tema abordado nesta dissertação de mestrado é a petrogênese dos diabásios do Eocretáceo que integram o Enxame de Diques da Serra do Mar na região de Angra dos Reis (RJ). Estes diques intrudem rochas do Terreno Ocidental e do Arco Magmático Rio Negro, inserindo-se no contexto geodinâmico de fragmentação do Gondwana no Cretáceo Inferior. Essas intrusões são subverticais e orientam-se preferencialmente a N039E. Intrusões retilíneas são as mais observadas em campo. Os diabásios são compostos, essencialmente, por plagioclásio e clinopiroxênios (augita e pigeonita). Quartzo, minerais opacos, apatita e olivina ocorrem como minerais acessórios. A composição mineral secundária é marcada pela presença de biotita, uralita e saussurita. Os diabásios estudados compreendem uma série transicional com afinidade toleítica. Os estudos petrológicos revelam a existência de cinco suítes de alto-TiO2, tendo sido as mesmas discriminadas com base nas razões La/Yb de amostras com o mesmo teor de MgO. Destas, apenas a suíte 2 têm quantidade mínima de amostras para avaliação de processos evolutivos. O resultado da modelagem petrogenética aponta que o processo evolutivo mais provável para a geração dos diabásios da suíte 2 é cristalização fracionada sem mudança na assembleia fracionante. As amostras representativas dos líquidos parentais das cinco suítes apresentam razões La/Nb e La/Yb maiores que a unidade, típicas de derivação de fonte enriquecida, que, em várias províncias basálticas continentais, tem sido associada à fusão exclusiva do manto litosférico subcontinental ou a sua participação em processos de mistura de fontes. A discriminação de fontes mantélicas foi feita exclusivamente com base nos teores de elementos traços de amostras representativas de líquidos parentais das cinco suítes discriminadas na área de estudo. Os modelos indicam que todas as cinco suítes estudadas estão relacionadas a fontes harzburgíticas com granada residual. A suíte 5 da área de estudo não pode ser associada à mesma fonte mantélica geradora das suítes 1, 2, 3 e 4 que, por sua vez, se originaram por diferentes quantidades de fusão parcial (respectivamente, 44%, 35%, 31% e 25%) de uma mesma fonte. Cabe ressaltar que a ocorrência de duas suítes, com razões La/Yb muito distintas, porém geograficamente muito próximas, sugere que processos de heterogeneidade mantélica, tipicamente laterais, devem também ocorrer verticalmente.

Ionic Liquids and Cellulose: Dissolution, Chemical Modification and Preparation of New Cellulosic Materials

Due to its abundance and a wide range of beneficial physical and chemical properties, cellulose has become very popular in order to produce materials for various applications. This review summarizes the recent advances in the development of new cellulose materials and technologies using ionic liquids. Dissolution of cellulose in ionic liquids has been used to develop new processing technologies, cellulose functionalization methods and new cellulose materials including blends, composites, fibers and ion gels.

Effects of chloride substitution on the chemical and physical properties and the crystallization behavior in heavy metal fluoride glasses

Effect of the substitutions of chloride for fluoride on the chemical and physical properties and the crystallization behavior in heavy metal fluoride glasses has been investigated. The characteristic temperature of the glass does not changed obviously when the fluoride was taken place by chloride. Compared with samples of being free of ErF3, the doping samples are more inclined to be surface crystallization. Optical basicity in the glass system increases with increasing the negative charge provided by the chloride atoms and the absorption peak red shifted is observed in absorption spectra. XRD measurements show that not a single crystalline phase appears in the heated glass samples, which indicate the substitutions of chloride for fluoride with a variety of crystalline precipitation trends. (c) 2007 Elsevier B.V All rights reserved.

Effect of Al(PO3)(3) content on physical, chemical and optical properties of fluorophosphate glasses for 2 mu m application

The effect of Al(PO3)(3) content on physical, chemical and optical properties of fluorophosphate glasses for 2 mu m application, such as thermal stability, chemical durability, surface hardness, absorption spectra and emission spectra, is investigated. With the increment of Al(PO3)(3) content, the thermal stability characterized by the gap of T-g and T,, increases first and then decreases, and reaches the maximum level containing 5 mol% Al(PO3)(3) content. The density and chemical durability decrease monotonously with the introduction of Al(PO3)(3) content increasing, while the refractive index and surface hardness increase. Above properties of fluorophosphate glasses are also compared with fluoride glasses and phosphate glasses. The Judd-Ofelt parameters, absorption and emission cross sections are discussed based on the absorption spectra of Tm-doped glasses. The emission spectra are also measured and the 1.8 mu m fluorescence of the sample is obvious indicating that it is suitable to 2 mu m application. (c) 2008 Elsevier B.V. All rights reserved.

Blue-yellow ZnO homostructural light-emitting diode realized by metalorganic chemical vapor deposition technique

We report on the realization of ZnO homojunction light-emitting diodes (LEDs) fabricated by metalorganic chemical vapor deposition on (0001) ZnO bulk substrate. The p-type ZnO epilayer was formed by nitrogen incorporation using N2O gas as oxidizing and doping sources. Distinct electroluminescence (EL) emissions in the blue and yellow regions were observed at room temperature by the naked eye under forward bias. The EL peak energy coincided with the photoluminescence peak energy of the ZnO epilayer, suggesting that the EL emissions emerge from the ZnO epilayer. In addition, the current-voltage and light output-voltage characteristics of ZnO homojunction LEDs have also been studied. (c) 2006 American Institute of Physics.

Demonstration of GaN/InGaN light emitting diodes on (100) beta-Ga2O3 substrates by metalorganic chemical vapour deposition

The growth and fabrication of GaN/InGaN multiple quantum well (MQW) light emitting diodes ( LEDs) on ( 100) beta-Ga2O3 single crystal substrates by metal-organic chemical vapour deposition (MOCVD) technique are reported. x-ray diffraction (XRD) theta-2 theta. scan spectroscopy is carried out on the GaN buffer layer grown on a ( 100) beta-Ga2O3 substrate. The spectrum presents several sharp peaks corresponding to the ( 100) beta-Ga2O3 and ( 004) GaN. High-quality ( 0002) GaN material is obtained. The emission characteristics of the GaN/InGaN MQW LED are measurement. The first green LED on beta-Ga2O3 with vertical current injection is demonstrated.

Structural and optical properties of a-plane ZnO thin films synthesized on γ-LiAlO2 (302) substrates by low pressure metal-organic chemical vapor deposition

Nonpolar a-plane (1120) ZnO thin films have been fabricated on gamma-LiAlO2 (302) substrates via the low-pressure metal-organic chemical vapor deposition. An obvious intensity variation of the E-2 mode in the Raman spectra indicates that there exhibits in-plane optical anisotropy in the a-plane ZnO thin films. Highly-oriented uniform grains of rectangular shape can be seen from the atomic force microscopy images, which mean that the lateral growth rate of the thin films is also anisotropic. It is demonstrated experimentally that a buffer layer deposited at a low temperature (200 degrees C) can improve the structural and optical properties of the epilayer to a large extent. (c) 2007 Elsevier B.V. All rights reserved.

Characterization of m-plane ZnO thin film on gamma-LiAlO2 (100) substrate by metal-organic chemical vapor deposition

Non-polar (1 (1) over bar 00)m-plane ZnO thin film has been prepared on gamma-LiAlO2 (100)substrate via the low pressure metal organic chemical vapor deposition. Obvious intensity variation of the E-2 mode in the polarized Raman spectra and the absorption edge shift in the polarized optical transmission spectra indicate that the m-plane film exhibits optical anisotropy, which have applications in certain optical devices, such as the UV modulator and polarization-dependent beam switch. From the atomic force microscopy images, highly-oriented uniform-sized grains of rectangular shape were observed. (c) 2008 Elsevier B.V. All rights reserved.